Metal component for fuel cell and method of manufacturing the same, austenitic stainless steel for polymer electrolyte fuel cell and metal component for fuel cell material and method of manufacturing the same , corrosion-resistant conductive component and method of manufacturing the same, and fuel cell

ABSTRACT

An Au plated film  12  is formed on the surface of a plate-formed metal base  13  composed of a metal less noble than Au, and the product is cut along a planned cutting line  18  reflecting a contour of a desired component, to thereby form a separator  10 . Thus-formed separator  10  has the Au plated film  12  formed on the main surface  10   a  thereof, and has a cutting plane  16  formed as an end face  16  stretched up to the main surface  10   a . The metal base  13  exposes in a part of the cutting plane  16 , in a width of the exposed region of 1 mm or less. This is successful in providing a metal component for fuel cell which is satisfactory in the corrosion resistance and allows easy fabrication at low costs, a method of manufacturing the same, and also in providing a fuel cell having thus-fabricated metal component for fuel cell.

TECHNICAL FIELD

A first invention relates to a metal component for fuel cell and amethod of manufacturing the same, and also to a fuel cell.

A second invention relates to an austenitic stainless steel for polymerelectrolyte fuel cell, and more specifically to an austenitic stainlesssteel for polymer electrolyte fuel cell used for conductive separator,current collector and so forth, and a metal component for fuel cellusing the same, and also to a fuel cell.

A third invention relates to a polymer electrolyte fuel cell materialsuch as a metal separator, current collector plate and so forth used inpolymer electrolyte fuel cell, and a method of manufacturing the same,and also to a metal component for fuel cell using the same and a fuelcell.

A fourth invention relates to a corrosion-resistant conductive materialrepresented by a metal separator for fuel cell, and a method ofmanufacturing the same, and also to a fuel cell.

BACKGROUND ART

(First Invention)

There are known fuel cells which include polymer electrolyte fuel cell,phosphoric-acid fuel cell, molten carbonate fuel cell and solid-oxidefuel cell. Of these, polymer electrolyte fuel cell, which is operable atlow temperatures and can readily be reduced in size and weight, is aimedat being mounted on such as fuel cell vehicle, stationary cogenerationsystem and mobile applications. In the polymer electrolyte fuel cell,the top and back surfaces of a polymer electrolyte film for transferringproton are held by a pair of electrodes on which carbon particles havinga platinum catalyst supported thereon are immobilized, and thus-obtainedmembrane/electrode assembly (MEA) is held between separators having gasdiffusion layer (carbon paper) and reaction gas supply grooves formedthereon, thereby a unit cell is formed. In general, a plurality of theunit cells are electrically connected in series so as to form a stack.The separator has surface of regular rough, formed thereon, forsupplying reaction gas so as to bring a fuel gas (hydrogen gas) or anoxidizer gas (air) into contact with the electrode, and is configured soas to allow the projected portions formed thereon to contact with thesurface of the electrode, and to allow the recessed portions to besupplied with the reaction gas. A conventional separator has been madeof carbon, but efforts have been also made on those made of metals, inview of realizing cost reduction, downsizing, and weight reduction ofthe fuel cell.

Adoption of the metal-made separators such as those made of stainlesssteel may raise a problem below. That is, a polymer electrolyte film ofa polymer electrolyte fuel cell contains sulfonic acid group, and needsmoisture in order to exhibit ion conductivity. Contact of the moisturewith the separator, however, lowers pH due to the sulfonic acid group,and this allows corrosion of the separator to proceed in a powergeneration environment of the fuel cell. Corrosion of the separatorresults in deterioration of the polymer electrolyte film due to elutedmetal ion, locally raises the electric resistance, and undesirablylowers the output of the fuel cell due to increase in the internalresistance.

Various efforts have therefore been made in view of prevent corrosion ofthe separator. For example, Japanese Laid-Open Patent Publication“Tokkai” No. 2001-68129, “Tokkai” No. 2000-021418 and “Tokkaihei” No.10-228914 disclose separators made of stainless steel having an Auplated film of a predetermined thickness formed on the surface thereof.Of these, the above publication “Tokkai” No. 2001-68129 discloses aseparator successfully reduced in influences of pinholes in the Auplated film formed on the surface of the separator, and thereby havingan improved corrosion resistance, by closing the pinholes by rollerpressing or resin molding. On the other hand, the publication“Tokkaihei” No. 10-228914 discloses a separator having an Au plated filmof relatively as thin as 0.01 to 0.06 μm partially formed in an area ofthe metal base composing the separator, to be brought into directcontact with the electrode, and thereby having a reduced contactresistance with the electrode while keeping a desirable level ofcorrosion resistance.

The separator disclosed in the publication “Tokkai” No. 2001-68129 is,however, fabricated by first forming an under-plated film prior to theAu plating, the Au plated film is then formed to a relatively largethickness in order to reduce the pinholes possibly formed in the Auplated film, and the obtained Au plated film is further roller-pressed,so that this inevitably increases the number of process steps of thefabrication, and also increases Au consumption. Also the separatordisclosed in the publication “Tokkaihei” No. 10-228914 isdisadvantageous in terms of simplification of the fabrication process,because the Au plated film is partially formed in the portion to bebrought into direct contact with the electrode. Moreover, the separatorhas no Au plated film in the recessed portions (which serves as a gasflow path) which are not brought into contact with the electrode, andthis may result in only a limited corrosion resistance against puddlesformed in the portions. Both of the separators for fuel cell disclosedin the publications “Tokkai” No. 2001-68129 and “Tokkaihei” No.10-228914 are fabricated by cutting a metal base to be processed intothe separators, and then subjecting them to the Au plating, but this isnot convenient in terms of fabrication process, because the individualseparated metal bases must be plated.

(Second Invention)

Because a metal separator for polymer electrolyte fuel cell allows anelectrode of a unit cell and another electrode of the adjacent unit cellto electrically contact with each other, and separates the reaction gas,it is necessary for the separator to have an excellent electricconductivity, an excellent gas tight performance to the reaction gas,and an excellent corrosion resistance against power generation reactionbased on a hydrogen/(oxygen or air) redox system.

There are known conventional metal separators for polymer electrolytefuel cells such as having a large number of regular rough patternedgrooves, for allowing the fuel gas or oxidizer gas to pass through,formed thereon by cutting carbon plates such as those composed ofgraphite or the like. The fabrication according to this method, however,suffers from increase in costs of the carbon materials and cuttingprocess, and this raises difficulty in practical application of theseparators in view of costs. Another problem resides in that the carbonplate cannot be thinned due to its poor strength, and therefore cannotbe reduced in size.

There have been developed metal separators for polymer electrolyte fuelcells, composed of a readily-machinable stainless steel having a treatedsurface. The publication “Tokkaihei” No. 10-228914 discloses use ofSUS304 as the stainless steel, and the publication “Tokkai” No.2000-021418 discloses use of SUS316. The publication “Tokkai” No.2000-256808 discloses a stainless steel for polymer electrolyte fuelcell containing 30% or less of Cr, and if necessary also at least eitherof Mo: 10% or less and Ni: 25% or less, and satisfies a relation of10−0.3×([Cr %]+3×[Mo %]+0.05×[Ni %])≦5, and the balance of mainly Fe.

As materials for composing the conductive separators forpolymer-electrolyte-type fuel cells, the publication “Tokkai” No.2001-243962 discloses a ferritic or an austenitic stainless steel havinga carbon content not exceeding 0.03%, a ferritic or an austeniticstainless steel having a carbon content of less than 0.03% and a Mocontent of 1.5 to 8%, an austenitic stainless steel having a carboncontent of 0.03% or less and a nitrogen content of 0.1 to 0.3%, and soforth.

The above-described SUS304 and SUS316 are, however, known to haveproblems in the corrosion resistance due to their large contents of C,Mn and S. The stainless steel disclosed in the publication “Tokkai” No:2001-243962 suffers from a poor machinability and a large cost, due toits substantially large Cr content, and also a large Mo content.

The separators for polymer electrolyte fuel cell is exposed to anextremely corrosive environment of sulfuric acid acidity and steam atabout 80° C. or more during power generation. An extremely highcorrosion resistance is therefore required for the separators. On theother hand, metal separators workable by plastic working intocomplicated geometry have also been developed for cost reduction,wherein the above-described corrosion resistance is required also forthis sort of separators.

Conventional measure for improving corrosion resistance of theseparators relates to use of a metal base plate composed of stainlesssteel or the like for configuring the separator, having the surface ofwhich covered with a cover film of a noble metal such as Au, Pt or thelike by plating and vacuum evaporation showing a higher corrosionresistance than that of the metal base.

In the formation of the cover film of a noble metal, the resultant coverfilm will have a surface of regular rough conforming to a fine surfaceof regular rough which intrinsically resides on the surface of the metalbase plate, but with an enphasized profile. In recessed portions on thesurface of such film, or in crystal grain boundary of the metal baseplate, the noble metal film is less depositable as compared with theprojected portions or other portions, and the film will therefore tendto be thinned. The recessed portions on the surface of the noble metalfilm and portions in the vicinity of the crystal grain boundary willtherefore show only a limited corrosion resistance, and this makes thecorrosion more likely to proceed from these portions towards the innerportion of the separator.

(Third Invention)

The separators for polymer electrolyte fuel cell is exposed to anextremely corrosive environment of sulfuric acid acidity and steam atabout 80° C. or more during power generation. An extremely highcorrosion resistance is therefore required for the separators. On theother hand, metal separators workable by plastic working intocomplicated geometry have also been developed for cost reduction,wherein the above-described corrosion resistance is required also forthis sort of separators.

Conventional measure for improving corrosion resistance of theseparators relates to use of a metal base plate composed of stainlesssteel or the like for configuring the separator, having the surface ofwhich covered with a cover film of a noble metal such as Au, Pt or thelike showing a higher corrosion resistance than that of the base elementby plating or vacuum evaporation.

In the formation of the cover film of a noble metal, the resultant coverfilm will have a surface of regular rough conforming to a fine surfaceof regular rough which intrinsically resides on the surface of the metalbase plate, but with an emphasized profile. In recessed portions on thesurface of such film, or in crystal grain boundary of the metal baseplate, the noble metal film is less depositable as compared with theprojected portions or other portions, and the film will therefore tendto be thinned.

The recessed portions on the surface of the noble metal film andportions in the vicinity of the crystal grain boundary will thereforeshow only a limited corrosion resistance, and this makes the corrosionmore likely to proceed from these portions towards the inner portion ofthe separator.

(Fourth Invention)

With respect to the metal separator and current collector for fuelcells, there is proposed a technique of forming a thin Au plated film onthe surface of a metal base such as stainless steel, in order to keep adesirable level of corrosion resistance and to lower the contactresistance (Japanese Laid-Open Patent Publication “Tokkaihei” No.10-228914). This sort of treatment is also effective for variousmaterials for electric contacts and terminals. According to theproposal, it is described that those having a Au plated film of 0.01 to0.06 μm thick directly formed on the stainless base show no Cr elutioneven after being subjected to nitric acid aeration test (JIS H8621) forone hour, and that this proves formation of no pinholes.

The metal separators in practical polymer electrolyte fuel cell will beexposed to more severe conditions such as a temperature of as high as100° C., so that higher corrosion resistance enough to prove no elutionof metal ions even under more severe test conditions is required, suchas under dipping in a boiling sulfuric acid solution of pH 2 for 168hours. Increase in the thickness of the plated film may substantiallysolve the problem, but the metal separators for fuel cell, used in aform of stack comprising a large number thereof, is not practical on thecost basis unless the thickness of the plated film is 100 nm or thinner.

The separators having a Au plated film (0.01 to 0.06 μm thick) formed onthe surface of the metal base, in particular of the stainless steelbase, by the Au plating process described in the aforementioned JapaneseLaid-Open Patent Publication “Tokkaihei” No. 10-228914, whichspecifically conforms to processes of “degreasing-->cleaning-->surfaceactivation-->cleaning-->Au plating-->cleaning-->drying”, however, wasfound to show elution of elements composing the metal base in thedipping test in a boiling sulfuric acid solution of pH 2 for 168 hours,and the amount of elution thereof was found to considerably vary case bycase. It is therefore obvious that a conductive material having anexcellent corrosion resistance equivalent to that of the metal separatoravailable for the polymer electrolyte fuel cell cannot be obtained onlyby subjecting the surface of the metal base to the Au plating accordingto any publicly-known methods.

Aiming at providing a conductive corrosion-resistant component durablein the above-described severe test, the present inventors made searchfor reasons for the poor corrosion resistance of the known Au-platedproducts, and reached the conclusions below:

the surface of the metal base and noble metal film plated thereoncontain a larger amount of impurities than expected, and these impairthe corrosion resistance of the film;

there is an intermediate layer containing the impurities at leastpartially between the noble metal film and metal base, and this lowersadhesiveness of the film per se to the metal base; and

the impurities are supposed to be incorporated before foreign films onthe surface of the metal base, such as passivation film, oxide film andcontamination film, which are harmful to corrosion resistance, arecompletely removed, and the noble metal film is directly formed thereon.

A conceptual expression of the above conclusions is given as an upperdrawing of FIG. 12. This is not a product of a mere imagination, but isexperimentally supported by Auger analysis which is given as a lowerdrawing of FIG. 12.

Residence of any foreign films and intermediate layer may result in thefollowing nonconformities:

foreign film components produce the pinholes in the noble metal film,which serve as initiation points of corrosion;

any sites of the intermediate layer having a small electric conductivitymay vary current density in electroplating, or locally worsens theuniformity, and this may increase the pinholes and reduce denseness ofthe film; and

a poor adhesiveness between the intermediate layer and noble metal filmmay readily result in separation of the noble metal film triggered bysome external impact.

It is therefore an object of the first invention to provide a metalcomponent for fuel cell which is satisfactory in the corrosionresistance and allows easy fabrication at low costs, and a method ofmanufacturing the same, and is further to provide a fuel cell havingthus-manufactured metal component for fuel cell.

An object of the second invention is to provide an austenitic stainlesssteel for polymer electrolyte fuel cell excellent in resistance againstsulfuric acid acidity.

An object of the third invention is to provide ahighly-corrosion-resistant, polymer electrolyte fuel cell material suchas metal separator, current collector and so forth, and a method ofmanufacturing a polymer electrolyte fuel cell material capable ofmanufacturing the same in a reliable manner.

An object of the fourth invention is to provide a corrosion-resistantconductive component, in particular metal separator for fuel cell,comprising a metal base and a noble metal film formed thereon,overcoming the aforementioned problems, being very few in the pinholes,dense in the film quality, excellent in the adhesiveness to the metalbase, and therefore being durable against severe conditions of use.

DISCLOSURE OF THE INVENTION

(First Invention)

A first aspect of the metal component for fuel cell of the firstinvention relates to a metal component for fuel cell, to be disposed incontact with a main cell unit comprising a polymer electrolyte film anda pair of electrodes holding it in between, which is configured ashaving a plate-formed metal base composed of a metal less noble than Au,and an Au film formed on the main surface thereof, and having a cuttingplane formed as an end face stretched up to the main surface, whereinthe cutting plane has a region of 1 mm or less in width having saidmetal base exposes therein.

A second aspect of the metal component for fuel cell of the firstinvention relates to metal component for fuel cell, to be disposed incontact with a main cell unit comprising a polymer electrolyte film anda pair of electrodes holding it in between, which is configured ashaving an Au film formed on the main surface of a plate-formed metalbase composed of a metal less noble than Au, and the metal base beingcut along a planned cutting line reflecting a contour of the component.

A first invention's method of manufacturing the above-described metalcomponents for fuel cell of the first and second aspects relates to amethod of manufacturing a metal component for fuel cell, to be disposedin contact with a main cell unit comprising a polymer electrolyte filmand a pair of electrodes holding it in between, comprising the steps offorming an Au film on the surface of a plate-formed metal base composedof a metal less noble than Au, and cutting the metal base along aplanned cutting line reflecting a contour of the component.

A possible reason why the conventional formation of the Au film on themetal base to be processed into a separator, in view of improving thecorrosion resistance, is carried out after the metal base is shaped intoa geometry of a separator, for example, may be as follows. That is,shaping of the metal base having the Au film formed thereon may causecrack in the Au film already formed thereon, or produce a cutting planeby cutting of the metal base, to thereby allow the metal base to exposein these regions, and corrosion is supposed to proceed in thus-exposedmetal base. In fact, the aforementioned patent publication discussesthat the pinholes formed in the Au plated film are regions where themetal base exposes and the corrosion thereof can proceed, so that thissort of exposure must be undesired.

The present inventors therefore made an experiment as described below.SUS316L was used as a material for composing the metal base, which isprocessed into the separator, an Au film of 100 nm thick or around wasformed on the surface of the metal base before the metal base is shapedinto the separator geometry, and the metal base is then dipped into acorrosive solution. The end face of the separator formed a cuttingplane, and had some region where the metal base exposes therein. Thecorrosive solution was a sulfuric acid solution of pH2, had atemperature of 100° C., and dipping time was set to 168 hours. Thecutting plane of the metal base after the experiment was observed. Nochange in color of the metal base was observed even it was exposed inthe cutting plane, and therefore no corrosion of the metal base wasobserved. The result indicates that the exposed region of the metalcomponent disposed in contact with the main unit of fuel cell is notalways corroded, even if the surface thereof is exposed to the corrosiveenvironment, provided that the Au film resides in the neighboringregion. The present inventors found out, as demonstrated by theabove-described experiment, that a metal component for fuel cell havinga satisfactory corrosion resistance can be obtained even if the metalbase is cut after the Au film is formed thereon, and the fact led us tothe first invention. Adoption of this method typically makes it possibleto form the Au film en bloc over a region of a relatively wide range,such as over the surface of a band-formed metal base, and thereby makesit possible to simplify a process of formation of the Au film. Inthus-manufactured metal component for fuel cell of the first invention,a desirable corrosion resistance can be ensured even if the metal baseexposes in the region to be brought into direct contact with theelectrode, or the region to be brought into direct contact with acorrosive environment such as a moisture-containing oxidizer gas (air,for example) atmosphere, so that it is no more necessary to roller-pressthe Au film after formation thereof, or to form the Au film to arelatively large thickness (1 μm or around, for example), in order tosuppress formation of the pinholes. This makes it possible to furtherfacilitate the manufacturing, reduces Au consumption, and to realize aninexpensive metal component for fuel cell. It was also found thatcorrosion of the metal base can sufficiently be suppressed if the widthof the surface of the metal base, exposed in the cutting plane of themetal component, is as wide as 1 mm or less. The width of the exposedsurface of the metal base exceeding 1 mm makes the exposed region of themetal base in the cutting plane too wide, and is unsuccessful inrealizing a sufficient level of corrosion resistance in the cuttingplane.

The metal components for fuel cell of the first and second aspects mayalso be configured as follows. That is, the electrode of fuel cell mayhave a plate form and is in contact with the solid polymer film on afirst main surface thereof, and the metal component may be configured asa separator disposed in contact with the electrode on a second mainsurface thereof, having a regular rough on the main surface opposing tothe electrode, wherein projected portions of the regular rough arebrought into contact with the electrode, and recessed portions of theregular rough serves as a gas flow path through which a fuel gas or anoxidizer gas is supplied to the electrode. The separator thus disposedin contact with the electrode of the main unit of the cell may possiblybe brought into contact with the fuel gas or oxidizer gas to be suppliedto the electrode. Moreover, the separator is a component very likely tobe corroded due to sulfate ion which may possibly be eluted from thepolymer electrolyte film. It is therefore particularly necessary for theseparator to be highly corrosion resistant, and the preferableapplication range specified in the first aspect of the first inventionmakes sense.

A third aspect of the metal component for fuel cell of the firstinvention relates to metal component for fuel cell, available as aseparator disposed in contact with a second main surface of aplate-formed electrode which is disposed in contact with a polymerelectrolyte film on a first main surface thereof, and has a regularrough on the main surface, opposing to the electrode, of a plate-formedmetal base composed of a metal less noble than Au, top portions ofprojected portions of the regular rough are brought into contact withthe electrode, and recessed portions of the regular rough serve as a gasflow path through which a fuel gas or an oxidizer gas is supplied to theelectrode, wherein the metal base has an Au film of 1 to 500 nm thickformed on both of the tip surface of the projected portions brought intocontact with the electrode, and the main surface region other than thetip surface.

Corrosion of the metal base will not proceed, as described in the above,even if the metal base exposes in the region susceptible to thecorrosion, such as in the region in direct contact with the electrode,but the region susceptible to the corrosion having absolutely no Au filmis unsuccessful in sufficiently preventing the metal base from beingcorroded. Therefore, the separator for fuel cell, such as beingdisclosed in Japanese Laid-Open Patent Publication “Tokkaihei” No.10-228914, disposed in contact with the electrode, and having a regularrough formed on the main surface on the side brought into contact withthe electrode, may be corroded in the recessed portions thereof which isnot brought into contact with the electrode and serve as a gas flow paththrough which the fuel gas or oxidizer gas are supplied to theelectrode, unless the recessed portions has the Au film formed thereon.The metal component for fuel cell according to the third aspect of thefirst invention is therefore designed to have the Au film which coversalso the region not brought into contact with the electrode, to therebysuppress the corrosion in such region. It is not always necessary forthe region not brought into contact with the electrode to be completelycovered with the Au film, wherein the exposed portions of the metalbase, such as pinholes, crack and so forth may remain. This allows thethickness of the Au film to be set to as relatively small as 500 nm orless, which tends to produce pinholes. The thickness of 1 nm or less is,however, not successful in satisfactorily preventing the corrosion ofthe metal base due to an extremely small amount of formation of the Aufilm. On the other hand, the thickness exceeding 500 nm increases Auconsumption and takes a longer time for the fabrication, and thisdeparts from the object of the first invention.

In thus-configured aforementioned metal component for fuel cell, areason why the metal base exposed in the region to be brought intoexposed to a corrosive environment, in which the corrosion shouldproceed in general, is not corroded is supposed as follows. Consideringnow arrangement of the individual components of the fuel cell, in whichthe Au film is formed and the metal base exposes in the regioncharacterized by a corrosive environment of the fuel cell, the metalbase and the Au film can configure a local cell. The local cell shiftsthe electrode potential of the metal base in the corrosive environmenttowards the passivity where the surface of the metal base is passivated,and thereby the corrosion of the surface of the metal base issuppressed.

Further detail will be given referring to FIG. 7A and FIG. 7B. FIG. 7Aschematically shows a potential-pH chart of a certain specific metalbase. For an exemplary case where the corrosive environment in which themetal component for fuel cell of the first invention is arranged has apH value of 1, and where only the metal base resides in the corrosiveenvironment, it is assumed now that the electrode potential. E (V) inreference to a hydrogen standard electrode has a value of E1 (V).Because electrode potential E1 under pH1 falls in the corrosion, themetal base in this situation will be corroded. Formation of the Au filmon the surface of the metal base, while leaving the metal base partiallyexposed in the corrosive environment, results in formation of a localcell in which the metal base functions as an anode, and the Au filmfunctions as a cathode. FIG. 7B shows an anode polarization curve “ia”and a cathode polarization curve “ic”. The Au film herein acts as acatalyst for promoting the cathode reaction at the cathode electrode.Increase in cathode reaction current shifts the cathode polarizationcurve “ic” towards the large current side, and raises the electrodepotential of the anode up to E2. If the electrode potential E2 falls inthe passivity as shown in FIG. 7A, corrosion of the metal base issuccessfully suppressed even when the metal base is exposed to anenvironment of pH1.

The metal base successfully suppressed in the corrosion based on theabove-described mechanism may be composed of a material capable offorming at least the active potential region and passive potentialregion in the anode polarization curve measured in an sulfuric acidsolution of pH1 at 80° C., and of showing an anode current in thepassivity of 100 μA/cm² or less. In other words, it is made possible,even in a corrosive environment, to raise potential of the metal basethrough formation of the local cell with the Au film as described in theabove and to bring the potential into the passivity, if there is atleast a potential range possibly shows passivity in the pH1 environment.

On the other hand, it is preferable to use the metal base such asshowing the active potential region in the anode polarization curveunder the pH1 condition. Absence of the active potential region underthe pH1 environment essentially indicates that the metal cannot becorroded in the environment. This sort of metal is generally expensive,so that it is undesirable to form the Au film on the metal base composedof such expensive metal, in view of suppressing increase in the cost.

An anode current density of 100 μA/cm² or less in the passive potentialrange makes it possible to suppress the corrosion rate to a sufficientlylow level, and to ensure a satisfactory level of corrosion resistance.

Suppression of the corrosion of the metal base is ascribable toformation of the local cell, based on contact between the Au film andmetal base in the corrosive environment. It is therefore also allowableto adopt a configuration in which the Au film is preliminarily formed onthe surface of a component which is possibly brought into contact withthe surface of the metal base of the metal component for fuel cell afterbeing incorporated into the fuel cell, so as to allow the metal base andAu film to contact with each other when the both are assembled toconfigure the fuel cell. For the metal component for fuel cell usedherein, it is necessary to adopt the metal base capable of forming thepassive potential region as described in the above, having no Au filmformed on the surface thereof.

It is still also possible to configure a fuel cell of the firstinvention, by using the above-described metal component for fuel cell ofthe first invention. That is, the fuel cell of the first invention has amain cell unit which comprises a solid polymer film as an electrolyteand a pair of electrodes holding it in between, and the metal componentfor fuel cell of the first invention. This sort of fuel cell issuccessful in suppressing the corrosion of the metal component for fuelcell used therefor, has a satisfactory lifetime, and is less likely tocause lowering in the obtainable output power. The fuel cell is alsoadvantageous in that it can be configured with less expensivecomponents, and consequently at low costs.

The metal component for fuel cell of the first invention may be such asbeing disposed in a sulfuric acid acidic environment of pH1 to 6 duringoperation of the fuel cell. Some cases use asulfonic-acid-group-containing film as the polymer electrolyte film. Thepolymer electrolyte film is used in a moist condition, and may thereforeelute sulfate ion. The metal component disposed in the vicinity of thepolymer electrolyte film may therefore be exposed to the sulfuric acidatmosphere, so that the metal component for fuel cell can be said ashaving a satisfactory level of corrosion resistance, only when itsucceeds in suppressing the corrosion of the metal component in thesulfuric acid atmosphere of pH1 to 6.

(Second Invention)

The present inventors investigated particularly into austeniticstainless steel for polymer electrolyte fuel cell excellent in sulfuricacid resistance, and found out that the sulfuric acid atmosphere in thevicinity of the electrode is created by water which is saturated undermoistening, in the polymer electrolyte film, which is used for thepolymer electrolyte fuel cell and contains sulfonic acid group; that itis necessary for the conductive separator to be excellent in the generalcorrosion resistance and particularly in the sulfuric acid resistance;and that more excellent sulfuric acid resistance can be exhibited bySUS304-base austenitic stainless steel added with Cu, or Cu togetherwith N, by SUSXM7-base austenitic stainless steel added with Mo and N,and by SUS316-base austenitic stainless steel added with N, Cu, or Ntogether with Cu.

The present inventors also found that the austenitic stainless steelhaving large impurity contents of C, Mn, P and S reduces its sulfuricacid resistance due to deposition of MnS, iron phosphides (Fe₃P, Fe₂P,FeP, FeP₃), chromium carbide (Cr₂₃Cr₆) and so forth in grain boundary;that manganese sulfide (MnS) can be reduced by limiting Mn content to1.00% or less, preferably to 0.45% or less, and S content to 0.005% orless; that chromium carbide (Cr₂₃Cr₆) can be reduced by liming Crcontent to less than 0.02%; that iron phosphide can be reduced bylimiting P content to 0.03% or less; and that an excellent sulfuric acidresistance can be obtained when the total of these impurities satisfiesa relation of 250×C %+5×Mn %+25×P %+200×S %<10.

The second invention was conceived based on these findings.

That is, an austenitic stainless steel for polymer electrolyte fuel cellof the second invention, in view of solving the aforementioned problem,consists essentially of Cu: 0.10-6.00%, Ni: 6.00-13.00%, Cr:16.00-20.00%, N: 0.005-0.30%, Si: 1.00% or less and Mn: 1.00% or less;and contains, if necessary, either one or both of Ti and Nb respectivelyin an amount of 1.20% or less and 5×[C %] or more; and the balance of Feand inevitable impurities.

Another aspect of the austenitic stainless steel for polymer electrolytefuel cell of the second invention consists essentially of Cu:0.10-6.00%, Ni: 6.00-13.00%, Cr: 16.00-20.00%, Mo: 0.10-4.00%, N:0.005-0.30%, Si: 1.00% or less and Mn: 1.00% or less; and contains, ifnecessary, either one or both of Ti and Nb respectively in an amount of1.20% or less and 5×[C %] or more; and the balance of Fe and inevitableimpurities.

Still another aspect of the austenitic stainless steel for polymerelectrolyte fuel cell of the second invention consists essentially ofCu: 0.10-6.00%, Ni: 10.00-15.00%, Cr: 16.00-18.50%, Mo: 1.00-4.00%, N:0.005-0.30%, Si: 1.00% or less and Mn: 1.00% or less; and contains, ifnecessary, either one or both of Ti and Nb respectively in an amount of1.20% or less and 5×[C %] or more; and the balance of Fe and inevitableimpurities.

Still another aspect of the austenitic stainless steel for polymerelectrolyte fuel cell of the second invention consists essentially ofCu: 0.10-6.00%, Ni: 6.00-13.00%, Cr: 16.00-20.00% and N: 0.005-0.30%;and contains, if necessary, either one or both of Ti and Nb respectivelyin an amount of 1.20% or less and 5×[C %] or more; and consists also ofC: less than 0.02%, Si: 1.00% or less, Mn: 1.00% or less, P: 0.030% orless and S: 0.005% or less, satisfying a relation of 250×[C %]+5×[Mn%]+25×[P %]+200×[S %]<10; and the balance of Fe and inevitableimpurities.

Still another aspect of the austenitic stainless steel for polymerelectrolyte fuel cell of the second invention consists essentially ofCu: 0.10-6.00%, more preferably 3.00-4.00%, Ni: 6.00-13.00%, Cr:16.00-20.00%, Mo: 0.10-4.00% and N: 0.005-0.30%; and contains, ifnecessary, either one or both of Ti and Nb respectively in an amount of1.20% or less and 5×[C %] or more; and consists also of C: less than0.02%, Si: 1.00% or less, Mn: 1.00% or less, P: 0.030% or less and S:0.005% or less, satisfying a relation of 250×[C %]+5×[Mn %]+25×[P%]+200×[S %]<10; and the balance of Fe and inevitable impurities.

Still another aspect of the austenitic stainless steel for polymerelectrolyte fuel cell of the second invention consists essentially ofCu: 0.10-6.00%, Ni: 10.00-15.00%, Cr: 16.00-18.50%, Mo: 1.00-4.00% andN: 0.005-0.30%; and contains, if necessary, either one or both of Ti andNb respectively in an amount of 1.20% or less and 5×[C %] or more; andconsists also of C: less than 0.02%, Si: 1.00% or less, Mn: 1.00% orless, P: 0.030% or less and S: 0.005% or less, satisfying a relation of250×[C %]+5×[Mn %]+25×[P %]+200×[S %]<10; and the balance of Fe andinevitable impurities.

A metal component for fuel cell of the second invention is configuredusing the austenitic stainless steel for polymer-type fuel cell of thesecond invention, and disposed in contact with a main cell unitcomprising a polymer electrolyte film and a pair of electrodes holdingit in between. More specifically, the electrode has a plate form and isin contact with the polymer electrolyte film on a first main surfacethereof, and the metal component is composed as a separator disposed incontact with the electrode on a second main surface thereof, and has aregular rough on the main surface opposing to the electrode, whereinprojected portions of the regular rough are brought into contact withthe electrode, and recessed portions of the regular rough serve as a gasflow path through which a fuel gas or an oxidizer gas is supplied to theelectrode. The fuel cell of the second invention has a main cell unitwhich comprises a polymer electrolyte film and a pair of electrodesholding it in between, and the metal component for fuel cell of thesecond invention.

The austenitic stainless steel for polymer electrolyte fuel cell of thesecond invention is improved in the sulfuric acid resistance necessaryfor the polymer electrolyte fuel cell, and in particular for theconductive separator, by allowing the publicly-known austeniticstainless steel to additionally contain any one of, or two or more ofCu, Mo and N.

Adjustment of C: less than 0.02%, Mn: 1.00% or less, P: 0.030% or lessand S: 0.005% or less, so as to satisfy a relation of 250×[C %]+5×[Mn%]+25×[P %]+200×[S %]<10, is successful in suppressing production ofmanganese sulfide, chromium carbide and iron phosphide which tend tolower the sulfuric acid resistance, and also in suppressing depositionthereof in the grain boundary, so that the austenitic stainless steel isimproved in the sulfuric acid resistance necessary in particular for theconductive separator.

The next paragraphs will detail the austenitic stainless steel forpolymer electrolyte fuel cell of the second invention (also simplyreferred to as “austenitic stainless steel of the second invention”,hereinafter). First, reasons for limitation on the composition of theaustenitic stainless steel of the second invention will be explained.

Cu: 0.10-6.00%

Cu produces austenitic phase capable of improving the corrosionresistance, contributes to stabilization of the austenitic phase, andimproves cold workability, and is added for these purposes. A content of0.10% or more is necessary for obtaining these effects, but an excessivecontent degrades the corrosion resistance and hot workability againstexpectation. The upper limit is therefore controlled to 6.00%.

Ni: 6.00-13.00%, 10.00-15.00%

Ni produces austenitic phase capable of improving the corrosionresistance, and contributes to stabilization of the austenitic phase,and is added for these purposes. A content of 6.00% or more is necessaryfor obtaining these effects for a composition of Cu: 0.10-6.00%, Cr:16.00-20.00% and Mo: 0.10-4.00%, or a content of 10.00% or more isnecessary for a composition of Cu: 0.10-6.00%, Cr: 16.00-18.50 and Mo:1.00-4.00%, but an excessive content degrades the strength and raisesthe cost. The upper limit is therefore controlled to 13.00% or 15.00%.

Cr: 16.00-20.00%, 16.00-18.50%

Cr improves the corrosion resistance and oxidation resistance, and isadded for these purposes. A content of 16.00% or more is necessary forobtaining these effects, but an excessive content degrades theworkability and makes the steel more likely to produce σ phase. Theupper limit is therefore set to 20.00% for a composition of Cu:0.10-6.00%, Ni: 6.00-13.00% and Mo: 0.10-4.00%; or set to 18.50% for acomposition of Cu: 0.10-6.00%, Ni: 10.00-15.00% and Mo: 1.00-4.00%

Mo: 0.10-4.00%, 1.00-4.00%

Mo improves the corrosion resistance and oxidation resistance, and isadded for these purposes. A content of 0.10% or more, optimally 0.5% ormore, is necessary for obtaining these effects for a composition of Cu:0.10-6.00%, Ni: 6.00-13.00% and Cr: 16.00-20.00%; or a content of 1.00%or more is necessary for a composition of Cu: 0.10-6.00%, Ni:10.00-15.00 and Cr: 16.00-18.50%, but an excessive content degrades thehot workability due to deposition of car phase, for example. The upperlimit is therefore controlled to 4.00%.

N: 0.005-0.30%

N produces austenitic phase capable of improving the corrosionresistance, and contributes to stabilization of the austenitic phase,and is added for these purposes. A content of 0.005% or more isnecessary for obtaining these effects, but an excessive content degradesthe workability. The upper limit is therefore controlled to 0.30%.

Ti: 5×C %-1.20%, Nb: 5×C %-1.20%

Ti and Nb micronize the crystal grain, increase the strength, andprevent solubilized amount of Cr in the host phase from decreasingthrough binding with C which undesirably decreases solubilized amount ofCr in the host phase, and are added for these purposes. A content of 5×C% or more is necessary for obtaining these effects, but an excessivecontent decreases the solubilized amount in solid of N through bindingwith N. The upper limit is therefore controlled to 1.20%.

C: Less than 0.02%

C is an interstitial element contributive to improvement in thestrength, but decreases solubilized amount of Cr in the host phasethrough binding with Cr to thereby form CrC, and this degrades thecorrosion resistance, in particular sulfuric acid resistance. Thecontent is preferably controlled to less than 0.02%.

Si: 1.00% or Less

Si is an element added as a deoxidizer during the melting, and also asan element for improving the anti-oxidation property, but an excessivecontent thereof degrades the hot workability. The content is preferablycontrolled to 1.0% or less.

Mn: 1.00% or Less

Mn produces austenitic phase capable of improving the corrosionresistance, and contributes to stabilization of the austenitic phase,but may produce MnS to thereby degrade the corrosion resistance, inparticular sulfuric acid resistance. The content is therefore controlledto 1.00% or less, and preferably 0.45% or less.

P: 0.030% or Less

P is an impurity, degrades the toughness and hot workability, andproduces iron phosphide in the grain boundary to thereby lower thetoughness and also lowers the corrosion resistance. The content istherefore controlled to 0.030% or less, and preferably 0.010% or less.

S: 0.005% or Less

S is an impurity, and produces MnS and FeS in the grain boundary tothereby degrade the corrosion resistance, in particular sulfuric acidresistance. The content is therefore controlled to 0.005% or less.

250×[C %]+5×[Mn %]+25×[P %]+200×[S %]<10

Because all of C, Mn, P and S are elements which may deposit in thegrain boundary to thereby degrade the sulfuric acid resistance, thecomposition is designed so that the formula in the above gives a valueof less than 10, because the value less than 10, as well as the contentsof the individual elements adjusted to the above-described ranges canfurther improve the sulfuric acid resistance.

Possible applications of the austenitic stainless steel of the secondinvention include conductive separator, current collector component andso forth for polymer electrolyte fuel cell, having a noble metal filmformed thereon, and used in a style as being covered with a noble metalfilm on the surface thereof.

The austenitic stainless steel of the second invention is used afterbeing reduced in the hardness typically by heating after or before thesurface thereof is covered with the noble metal film, so that it can beshaped, with an excellent process accuracy, into the conductiveseparator, current collector component and so forth for polymerelectrolyte fuel cell.

Next, a method of manufacturing the austenitic stainless steel of thesecond invention will be explained.

The austenitic stainless steel of the second invention has a compositionof SUS304, 304L, XM7, 316 or 316L, added with any one of, or two or moreof Cu, Mo and N, or added with the above element(s) together with C:less than 0.02%, Mn: 1.0% or less, P: 0.030% or less and S: 0.005% orless, so that it can be manufactured similarly to SUS304, 304L, XM7, 316or 316L.

(Third Invention)

The third invention was conceived after our extensive investigations andresearches, based on an idea of reducing surface roughness of a coverfilm of a noble metal formed so as to cover the metal base, bysmoothening through rolling and compressing, or by forming the noblemetal film after the surface of the metal base plate is smoothened. Thatis, the polymer electrolyte fuel cell material of the third inventioncomprises a plate material composed of an Fe-base alloy, Ni-base alloy,Ti or Ti-base alloy, and a cover film of a noble metal covering thesurface thereof, wherein the cover film on the plate material has asurface roughness as expressed in R_(max) of 1.5 μm or less.

Examples of the above-described Fe-base alloy include common steel,various special steels, stainless steel and Fe—Ni-base alloys; examplesof the above-described Ni-base alloy include Inconel 800, ditto 825,ditto 600, ditto 625, ditto 690, Hastelloy C276 and NCH1; and examplesof the above-described Ti-base alloy include Ti—22 wt % V—4 wt % Al,Ti—0.2 wt % Pd and Ti—6 wt % Al—4 wt % V. Examples of the noble metalinclude Au, Ag, Pt, Pd, Rh and Ir, and alloy having any of theseelements as a base element. The surface of the plate material denotes atleast either one of the top surface and back surface. Examples of thecell material include separator, current collector plate, processedplate and so forth for the cell.

The plate material generally has a micro-irregularities formed on thesurface thereof, due to transfer of regular roughs on thecircumferential surface of the rolling roll, and loss of the metalcomponent caused by surface treatment such as acid cleaning or by heattreatment such as annealing. It is also anticipated that the noble metalfilm is less adhesive to the grain boundary of the plate material, wheredeposits such as carbide and sulfide, and impurity elements arecondensed. The above-described cell material will have the surface ofregular rough conforming to the micro-irregularity of the surface of theplate material, and having an emphasized profile, formed once on thesurface of the noble metal film, but the surface regular rough issmoothened by compression typically by rolling described later. What isbetter, the surface of the noble metal film is as smooth as having ansurface roughness as expressed in R_(max) of 1.5 μm or less, the naturalpotential is averaged over the entire surface, wherein the recessedportions having only a thin film formed thereon are supplied with thefilm from the projected portions, and thereby the thickness and theplate material per se is smoothened. As a consequence, the surface ofthe film no more has a portion where the thickness thereof is extremelysmall, and can exhibit an excellent corrosion resistance. Anotherpossible process is such that the surface of the plate material used asa base is subjected, before being covered with the cover film of a noblemetal, electrolytic polishing to thereby smoothen the surface andaverage the regular rough, and this is successful in obtaining theeffect similarly to as described in the above, because the surface ofthe plate material is planarized together with the noble metal film,after coverage with a noble metal.

The cell material of the third invention also includes a polymerelectrolyte fuel cell material which shows, in an anti-corrosion test,an amount of Fe ion elution of 0.15 mg/0.4 liter or less, and an amountof Ni ion elution of 0.01 mg/0.4 liter or less. According to theinvention, the cell material can exhibit an excellent corrosionresistance in a more reliable manner even when it is exposed to anextremely corrosive environment for a long duration of time as aseparator or current collector plate of the cell. The amount of Fe ionelution exceeding 0.15 mg/0.4 liter or the amount of Ni ion elutionexceeding 0.01 mg/0.4 will result in the cell material having only aninsufficient corrosion resistance for the practical use, so that theabove-described allowable ranges of the elution are determined so as toavoid the undesirable ranges.

A first method of manufacturing a polymer electrolyte fuel cell materialof the third invention comprises a coverage step of forming a cover filmof a noble metal so as to cover the surface of a plate material composedof an Fe-base alloy, Ni-base alloy, Ti or Ti-base alloy; and a rollingstep of rolling the plate material having the surface covered with thecover film of a noble metal, between a pair of rolls having a surfaceroughness as expressed in R_(max) of 1.5 μm or less. The method makes itpossible to fabricate the cell material covered with the noble metallayer and having a smooth surface in a reliable-and-efficient manner.The above-described coverage step using a noble metal is carried out byplating, vacuum evaporation and so forth.

The third invention also includes a method of manufacturing a polymerelectrolyte fuel cell material, in which the above-described rollingstep is carried out under a draft of 1% or more. This makes it possibleto smoothen the surface of the cover film of a noble metal, which isformed with a micro-irregularity on the surface of the plate material,such as having a surface roughness as expressed in R_(max) of as smallas 1.5 μm or less in a reliable manner. The draft less than 1% maysometimes fail in suppressing the surface roughness as expressed inR_(max) of the cover film of a noble metal formed so as to cover theplate material to as small as 1.5 μm, so that this case is omitted. Infurther detail, a desirable range of the draft is 5 to 50%, morepreferably 10 to 30%, and 80% in maximum.

The second method of manufacturing a polymer electrolyte fuel cellmaterial of the third invention comprises a smoothening step ofsmoothening a plate material composed of an Fe-base alloy, Ni-basealloy, Ti or Ti-base alloy so as to attain a surface roughness asexpressed in R_(max) of 1.5 μm or less; and a coverage step of forming anoble metal film so as to cover the surface of the plate material.Because the surface of the plate material per se is preliminarilysmoothened in this method, the cover film of a noble metal can be formedin a smooth and more uniform manner.

The above-described smoothening step can adopt electrolytic polishing orrolling using rolls having a surface roughness as expressed in R_(max)of 1.5 μm or less, and thereby, it is made possible to adjust a surfaceroughness as expressed in R_(max) of the plate material to as small as1.5 μm or less. The rolling using the rolls having R_(max) of 1.5 μm orless, carried out after the smoothening and the coverage with the noblemetal film, makes it possible to obtain a film having a more uniformthickness and a more excellent adhesiveness. The draft in this case maybe the same as described in the above.

A metal component for fuel cell of the third invention is configured byusing the austenitic stainless steel for polymer electrolyte fuel cellof the third invention, and is to be disposed in contact with a maincell unit comprising a polymer electrolyte film and a pair of electrodesholding it in between. More specifically, the electrode has a plate formand is in contact with the polymer electrolyte film on a first mainsurface thereof, and the metal component is composed as a separatordisposed in contact with the electrode on a second main surface thereof,having a regular rough on the main surface opposing to the electrode,projected portions of the regular rough being brought into contact withthe electrode, and recessed portions of the regular rough serving as agas flow path through which a fuel gas or an oxidizer gas is supplied tothe electrode. A fuel cell of the third invention has a main cell unitwhich comprises a polymer electrolyte film and a pair of electrodesholding it in between, and the metal component for fuel cell of thethird invention.

(Fourth Invention)

A corrosion-resistant conductive component of the fourth inventioncomprises a metal base and a noble metal film of 100 nm thick or lessformed on at least a part of the surface of the metal base, wherein thenoble metal layer and an intermediate layer formed between the base andthe noble metal layer have impurity contents of C: 1.5% or less, P: 1.5%or less, O: 1.5% or less and S: 1.5% or less, which are restricted toC+P+O+S: 4.0% or less. Meanings of these limitative values will besupported by practical data described later. The fuel cell of the fourthinvention has a main cell unit which comprises a polymer electrolytefilm and a pair of electrodes holding it in between, and the metalseparator for fuel cell composed of the corrosion resistant conductivecomponent of the fourth invention.

A fourth invention's method of manufacturing the corrosion resistantconductive component having the noble metal film of a low impuritycontent comprises the steps of removing a contamination film whichresides on the surface of the metal base by physical and/or chemicalprocesses so as to allow a clean surface to expose, and forming thereona cover film of a noble metal immediately thereafter, before the surfaceis contaminated again.

The base metal can arbitrarily be selected from those which cancompletely be covered with a noble metal in portions of the surface forwhich corrosion resistance is required, wherein it is advantageous thatthe base per se has a certain level of corrosion resistance. In thispoint of view, stainless steel, in particular austenitic stainless steelexcellent in the corrosion resistance, is preferable.

Use of the austenitic stainless steel for the base allows Fe, Cr and Ni,which are major components thereof, to appear in the intermediate layerbetween the base and noble metal layer, and even in the noble metallayer. It was made clear that ratio of contents of these elements, thusappear in the noble metal layer and in the intermediate layer, isparticularly important for the corrosion resistance. More specifically,the noble metal layer and the intermediate layer preferably have amaximum Cr/Fe ratio of 3 or less, and a maximum Ni/Fe ratio of 2 orless. This is also supported by data described below.

The noble metal composing the noble metal film may be any one elementselected from Au, Pt, Pd, Rh and Ru, and mixtures of these elements. Itstill may be alloys mainly composed of these elements, so far as theykeep characteristics of noble metal.

Both of wet and dry processes are applicable as the physical and/orchemical processes of removing a contamination film, which resides onthe surface of the metal base and composed of foreign matters such aspassivation film and oxide film, so as to allow a clean surface toexpose. A representative process of the former is cleaning using anelectrolytic polishing solution, and a representative process of thelatter is vacuum ion irradiation. The “electrolytic polishing solution”includes not only those generally used for electrolytic polishing, butalso corrosive solution such as a 20% sulfuric acid solution.

The phase of “immediately thereafter, before the surface is contaminatedagain” means, for the case of stainless steel, an interval of time “fromremoval of the surface passivation film to re-formation of thepassivation film”, and this is preferably short as possible. In aspecific way of speaking referring to the actual operations, it isnecessary to start the formation of the noble metal film within oneminute or around, whichever process of wet or dry should be used for thecleaning. In view of shortening the interval, the cleaning carried outby the wet process is preferably followed by the formation of the noblemetal film again based on the wet process, such as electroplating orelectroless plating, and the cleaning carried out by the dry process ispreferably followed by the formation of the noble metal film again basedon the dry process, such as sputtering or ion-assisted vacuumevaporation, which are categorized in vacuum film growth process.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing showing an exemplary configuration of afuel cell of the first invention;

FIG. 2A is a first schematic drawing showing an exemplary configurationof a metal component for fuel cell of the first invention;

FIG. 2B is a second schematic drawing showing an exemplary configurationof the metal component for fuel cell of the first invention;

FIG. 2C is a third schematic drawing showing an exemplary configurationof the metal component for fuel cell of the first invention;

FIG. 3 is a schematic drawing showing an apparatus for forming an Aufilm on the surface of a metal base;

FIG. 4 is a schematic drawing conceptually showing a fabrication methodof the first invention;

FIG. 5A is a drawing showing a first example of method of cutting aband-formed component;

FIG. 5B is a drawing showing a second example of method of cutting aband-formed component;

FIG. 6A is a drawing showing a third example of method of cutting aband-formed component;

FIG. 6B is a drawing showing a fourth example of method of cutting aband-formed component;

FIG. 7A is a first drawing explaining a mechanism of preventingcorrosion of a metal base;

FIG. 7B is a second drawing explaining a mechanism of preventingcorrosion of a metal base;

FIG. 8 is a schematic drawing showing an exemplary mode of contactbetween the surface of a separator and an Au film;

FIG. 9A is a perspective view of a separator as an exemplary mode of thecell material of a third invention;

FIG. 9B is an enlarged sectional view of portion B surrounded by adashed line in FIG. 9A;

FIG. 9C is an enlarged view of portion C surrounded by a dashed line inFIG. 9B;

FIG. 10A is a schematic drawing showing a process step of manufacturingthe cell material of the third invention;

FIG. 10B is a schematic drawing showing a succeeding process step ascontinued from FIG. 10A;

FIG. 10C is an enlarged view of portion C surrounded by a dashed line inFIG. 10B;

FIG. 11A is a schematic drawing showing a succeeding process step ascontinued from FIG. 10B;

FIG. 11B is an enlarged sectional view of portion B surrounded by adashed line in FIG. 11A; and

FIG. 12 is a drawing showing surface state of a corrosion-resistantconductive component comprising a metal base and a noble metal filmformed thereon, wherein the upper half shows a schematic sectional view,and the lower half shows a graph of a correspondent Auger profile.

BEST MODES FOR CARRYING OUT THE INVENTION

FIG. 1 explains the outlines of a metal separator for fuel cell commonlyapplicable to the first, second, third and fourth inventions, and anexemplary mode of a fuel cell using the same. The fuel cell 1 is apolymer electrolyte fuel cell adopting a polymer electrolyte film 3.More specifically, the polymer electrolyte film 3 may be composed of afluorine-containing resin containing sulfonic acid groups. The fuel cell1 has a polymer electrolyte film 3 and a pair of electrodes 2, 4 holdingit in between, and therefore has a main cell unit 5 which comprises thepolymer electrolyte film 3 and the electrodes 2, 4. The electrodes 2, 4are brought into contact with the polymer electrolyte film 3 on theirfirst main surfaces 2 a, 4 a, and plate-formed separators 10 aredisposed on the outer sides of the electrodes 2, 4 so as to be broughtinto contact therewith on their second main surfaces 2 b, 4 b. Each ofthe separators 10 plays a role of connecting the main cell units 5 inseries, and is disposed so as to supply a fuel gas and oxidizer gas tothe main cell unit 5. In this mode of embodiment, the separator 10corresponds to a metal component for fuel gas of the first invention. Itis to be noted that a gasket, not shown in FIG. 1, is disposed betweenthe main cell unit 5 and each of the separators 10 in order to preventleakage of the fuel gas and oxidizer gas. The main cell unit 5 and theseparators 10 composes a unit cell U, and a plurality of the unit cellsU are stacked while individually placing a cooling water flowingsubstrate 11 (composed of a conductive material such as graphite) inbetween, to thereby configure a fuel cell stack 1. The unit cells U arestacked in, for example, the number of 50 to 400 or around, andrespectively on both ends of the stack, there are disposed, as viewedfrom the side in contact with the unit cell U, a conductive sheet 9, acurrent collector plate 8, an insulating sheet 7, and a tightening plate6, to thereby configure a fuel cell stack 1. The current collector plate8 and a plurality of separators 10 are connected in series, so as tocollect current from a plurality of main cell units 5. It is defined nowthat the above-described unit cell U and fuel cell stack 1 are alsoincluded in the concept of the fuel cell in this patent specification.It is to be noted that FIG. 1 shows the individual components, includingthe conductive sheet 9, current collector plate 8, insulating sheet 7and tightening plate 6, are illustrated as being departed from eachother, but these components in practice are tightened with each otherusing bolts, for example.

FIG. 2A to FIG. 2C show the outlines of the separator 10. As shown inFIG. 2A, the separators 10 are shaped in a plate form, have a regularrough formed on the main surfaces thereof, and are disposed so as tomake the end sides of the projected portions 14 of the separators 10contact with the electrodes 2, 4. The recessed portions of eachseparator 10 serve as gas a flow path 21 (see also FIG. 1) through whicha fuel gas or an oxidizer gas is supplied to the electrodes 2, 4. Thegas flow path 21 has openings formed on both ends thereof, which serveas a reaction gas inlet port 22 and a reaction gas outlet port 23,respectively. The separators 10 are stacked so that the reaction gasinlet ports 22 and reaction gas outlet ports 23 formed on the individualseparators 10 are aligned at the same positions.

The paragraphs below will describe modes of embodiments specific to theindividual inventions.

(First Invention)

As shown in FIG. 2B, the separator 10 comprises a metal base 13 and anAu film 12 formed on the main surface thereof, wherein the Au film 12 isformed not only on top surfaces 14 a of the projected portions 14, butalso on the side faces 15 a and bottoms 15 b of the recessed portions 15(non-contact regions) which are not planned to contact with theelectrodes 2, 4. Thickness of the Au film 12 is adjusted to 1 to 500 nm.The Au film 12 is an Au-plated film 12.

Defining now the region of the metal base 13 not brought into contactwith the electrodes 2, 4 is non-contact region, 90% or more of thenon-contact region is provided as an Au-plated region having the Auplated film 12 formed thereon. Because the Au-plated film 12 is thusformed in 90% or more of the non-contact region with the electrode, therecessed portions, through which the fuel gas or the oxidizer gas flows,is successfully suppressed in the corrosion due to the oxidizer gas, ordue to sulfuric acid ion eluted from the polymer electrolyte film 3.

The separator 10 has, as shown in FIG. 2C, a cutting plane 16 as an endface 16 stretched up to the main surface 10 a. The cutting plane 16 hasa region where the Au plated film 12 is not formed thereon, and themetal base 13 of the separator 10 is therefore exposed therein. Width ofthe region where the metal base 13 exposes is adjusted to 1 mm or less.

The metal base 13 composing the separator 10 shows, as described in theabove, at least the active potential region and passive potential regionin the anode polarization curve shown in FIG. 7B, measured under a pH1condition.

The Au plated film 12 is formed directly on the metal base 13. Auplating on the surface of a metal generally needs an under-plated filmformed between the metal base and Au plated film 12. The under-platedfilm contributes to formation of the Au plated film 12 having nopinholes or the like formed therein. However in the first invention,there is no need of suppressing the pinholes formed in the Au platedfilm, and the Au film can directly be formed without forming theunder-plated film. Thus-formed separator 10 as a metal component forfuel cell is therefore configured so that exposed regions of the metalbase 13 are formed in a discrete manner in the Au plated region havingthe Au plated film 12 formed therein. This simplifies the fabricationprocess and successfully reduces the cost.

The metal base 13 can specifically be configured as containing at leastCr. Cr is a well-known passivation metal, and the metal base 13containing Cr can form the passivation potential region in the anodepolarization curve as shown in FIG. 7B. It is more preferable herein tosatisfy a relation of W_(Cr)+3.3W_(Mo)≧10, where W_(Cr) (% by weight) isCr content, and W_(Mo) (% by weight) is Mo content. In this way, also Mocapable of promoting passivation of metal may be contained in the metalbase 13, in addition to Cr. Assuming now W_(Cr)+3.3W_(Mo) as passivationperformance, a passivation performance of 10% or more by weight isenough to shift the electrode potential into the passivation potentialregion, even if the metal base is exposed to a corrosive environment ofpH1, by virtue of formation of a local cell with the Au plated film 12.The Fe-base alloy for composing the metal base 13 may also be, inparticular, stainless steel. The metal base 13 may still also becomposed of Ti, or Ti-base alloy.

Specific examples which can be adopted as metal base of the stainlesssteel; Fe-base alloy or Ni-base alloy; and Ti or Ti-base alloy will beenumerated below:

Ti or Ti-base alloy: pure Ti, Ti—22V—4Al;

stainless steel: SUS430, SUS304, SUS305, SUSXM7, SUS316, SUS316L,SUS317, SUS317L, SUS317J1, SUS310S and SUSJ5L;

Fe-base alloy: Incoloy 800; and

Ni-base alloy: Inconel 600, NCH1.

Next paragraphs will explain a method of manufacturing theabove-described separator 10. It is to be noted that the metal base 13is preliminarily formed in a band form. The Au film 12 is formed on themain surface of the band-formed metal base 13, and the metal base 13 isthen shaped into the separator 10. The Au film can be formed byelectroplating. FIG. 3 shows the outlines of an apparatus for formingthe Au film 12 by electroplating on the band-formed metal base 17. Aplating bath B has a plating solution SL contained therein. The platingsolution SL for forming the Au plated film 12 can typically be composedof a gold potassium cyanide solution, while being not limited thereto.The band-formed metal base 17 is introduced from an feeding roll 50 intothe plating bath B, and allowed it to run between electrodes 55, 55which are held in the plating bath B and supplied with current, andthereby the Au plated film 12 can be formed on the surface ofthus-introduced metal base 17. Bath temperature, concentration of thesolution, feeding speed of the metal base 17 and so forth herein areappropriately adjusted so that the Au plated film 12 is formed to athickness of 1 to 500 nm. Formation of the Au plated film 12 on theband-formed metal base 17 before being processed makes it possible toform the Au plated film 12 over a wide area at a time, and this ishopeful for an improved efficiency in the manufacturing. In this mode ofembodiment in no need of selectively forming the Au plated film 12, anyspecial treatment therefor is not necessary at all, and thereby the Auplated film 12 is formed over the entire portion of the main surface ofthe metal base 17.

After the Au plated film 12 is formed on the band-formed metal base 17as described in the above, the metal base 17 is then cut along a plannedcutting line 18 reflecting a contour of the separator 10, as shown inFIG. 4. The metal base 10, having the cutting plane 16 formed as an endface 16 stretched up to said main surface 10 a, is thus obtained. Theindividual metal bases 10 thus cut out are pressed so as to form theregular rough on the main surface thereof, and thereby the separators 10for fuel cell can be obtained.

In this mode of embodiment, the metal base 17 is cut, as shown in FIG.5A, by placing the band-formed metal base 17 on a stage 20, placing acutting edge 19 on the surface of the metal base 17, and by pressing thecutting edge 19 into the metal base 17 to thereby effect cutting. Bythis process, the Au plated film 12 extends along the end face 16, whichis formed as a cutting plane 16, of the metal base 13 so as to cover apart of the end face 16. In particular, the above-described process issuccessful in narrowing the width of a region, where the metal base 13exposes, in the cutting plane 16 (end face 16) to as small as 1 mm orless. As is clear from the above, in this mode of embodiment, the mostpart of the cutting plane 16 (end face 16) is covered with the Au platedfilm 12, and a minimum area of the metal base 13 is exposed in a part ofthe cutting plane 16 (end face 16). When the metal base 13 having the Auplated film 12 formed thereon is cut, it is also allowable, as shown inFIG. 5B, to place the cutting edges 19 on both main surfaces of theband-formed metal base 17, and the opposing cutting edges 19 are thenbrought closer to each other, to thereby cut the metal base 17. Thismakes it possible to further reduce the amount of exposure smaller thanthat in the method shown in FIG. 5A.

For the case where the metal base 13 is cut from both surfaces thereofby the cutting edges 19, it is also allowable to adopt a method shown inFIG. 6A. That is, the metal base is preliminarily thinned, using acompression member 25, in the vicinity of the planned cutting line asshown in FIG. 4, and the cutting edges 19 are placed on the thinnedplanned cutting line, and the metal base is the cut. The separator forfuel cell will have, formed therein, also openings such as gas flow port23, and alignment holes for the convenience of stacking. This sort ofopening can be formed by preliminarily thinning a region around a siteof formation of the opening by means of the compression member 25, andthen by punching the region off using a press machine 26 as shown inFIG. 6B. For the case where the region around the planned cutting lineis thinned as described in the above, it is preferable to thin the metalbase 13 to as thin as 0.1 mm or less. The methods shown in FIGS. 6A and6B make it possible to narrow the width of exposed surface of the metalbase 13 in the end face 16 of the separator 10 or in the end face 28 ofthe opening 27 to as small as 1 mm or less, and further to as small as0.1 mm or less.

For the case where the opening 27 is formed by the above-describedmethod shown in FIG. 6B, it is preferable to use a rod component 29,having a nearly similar geometry with that of the opening 27 to beformed but larger in the cross-sectional geometry, as being insertedinto the opening 27 so that the sectional geometry corresponds with thegeometry of the opening 27. This makes the edge of the opening 27 foldedin the direction of insertion of the rod component 29, and makes itpossible to further reduce the exposed region of the metal base 13 inthe end face 28 of the opening 27. It is even possible to completelyhide the metal base 13. It is to be noted that, also for the case shownin FIG. 6A, the edge can be rounded in a similar manner.

Although the present mode of embodiment explains the separator 10 as themetal component for fuel cell, the first invention is by no meanslimited thereto, and is applicable to any other metal components whichare used for fuel cells and possibly corroded.

Suppression of the corrosion of the metal base 13 is ascribable toformation of the local cell, based on contact between the Au film 12 andmetal base 13 in the corrosive environment. It is therefore alsoallowable, when the metal base 13, which is the metal component for fuelcell, is incorporated into the fuel cell, to adopt a configuration inwhich the Au film 12 is preliminarily formed on the surface of acomponent which is possibly brought into contact with the surface of themetal base 13, so as to allow the metal base 13 and Au film 12 tocontact with each other when the both are assembled to configure thefuel cell. For the metal component for fuel cell used herein, it is alsoallowable to adopt the metal base 13 capable of forming the passivepotential region in the anode polarization curve measured under the pH1condition as described in the above, having no Au film 12 formed on thesurface thereof.

That is, a fuel cell 1 adoptable herein is such as having a main cellunit 5 which comprises a polymer electrolyte film 3 as an electrolyteand a pair of electrodes 2, 4 holding it in between, and having a metalcomponent as the metal component for fuel cell, wherein a metalcatalyst, which is noble than the metal composing the surficial portionof the metal component and is capable of activating oxygen reducingreaction and hydrogen ion reducing reaction in the corrosion reactionwhich proceed on the surficial portion of the metal component, isimmobilized on the surface of a support which is a separate componentfrom the metal member, and the metal member is brought into contact withthe support component while placing the metal catalyst in between.

Referring now to the case where the metal component is the separator 10,the following configuration can be adopted. That is, in the unit cell Ushown in FIG. 1, a gas diffusion layer 32 is provided, as shown in FIG.8, to each of the electrodes 2, 4 on the side thereof brought intocontact with the separator 10, and a film of Au as the metal catalyst isformed on each of the gas diffusion layers 32 on the side thereofbrought into contact with the separator 10. Contact of the Au film 30with the surface of the separator 10 forms a local cell, and therebycorrosion of the separator 10 can be suppressed even when the separator10 is in direct contact with moisture contained in the polymerelectrolyte film 3 or with the oxidizer gas. The gas diffusion layer 32herein functions as the support.

The gas diffusion layer 30 is provided so as to allow the fuel gas oroxidizer gas, supplied through the recessed portions 15 (gas flow path21) to the electrodes 2, 4 of the separator 10, to enter a catalystlayer 31 provided on each of the electrodes 2, 4 on the side thereof incontact with the polymer electrolyte film 3, from a more wide area. Whenthe fuel gas or oxidizer gas passed through the gas diffusion layer 30reaches and enters the catalyst layer 31, the gases are oxidized orreduced to thereby produce electromotive force. The catalyst layer 31has, as being immobilized thereon, the catalyst for activating the cellreactions (oxidation reaction at the anode and reduction reaction at thecathode) at the electrodes 2, 4. Pt is the catalyst adopted herein inthis mode of embodiment, as the catalyst for activating the cellreactions.

The Au film 30 can be configured using a porous material on the gasdiffusion layer 32. This is because the Au film 30 should not interceptthe passage of the fuel gas and oxidizer gas. For this reason, the metalcatalyst 30 is partially brought into contact with the surface of theseparator 10 in the portions (top surfaces of the projected portions 14of the separator 10) where the gas diffusion layer 32 and separator 10are brought into contact.

It is also allowable to exemplify a configuration in which anunillustrated porous conductive sheet is disposed respectively betweenthe electrodes 2, 4 and separator 10 so as to respectively contact withthe electrodes 2, 4 and separator 10, a film of Au as the metal catalystis formed on the porous conductive sheet on the surface thereof incontact with the separator 10, to thereby use the porous conductivesheet as the support.

It is still also allowable to configure the porous conductive sheet suchas being composed of a metal less noble than Au as the metal catalyst,and as having the Au films supported on both surfaces of the porousconductive sheet. The porous conductive sheet herein can be composed ofan alloy of a metal less noble than Au as the metal catalyst and themetal catalyst (Au).

It is still also allowable to form the gas diffusion layer on theelectrodes on the sides thereof in contact with the separators, andthereby the gas diffusion layer is formed as the porous conductivesheet.

(Second Invention)

This invention relates mainly to material characters, and will bedetailed later referring to experimental results. Specific examples ofthe metal separator for fuel cell and fuel cell using the same wereexplained previously referring to FIG. 1 and FIG. 2A to FIG. 2C, asembodiments common for those of other inventions.

(Third Invention)

Specific examples of the metal separator for fuel cell and a fuel cellusing the same were explained previously referring to FIG. 1 and FIG. 2Ato FIG. 2C, as embodiments common for those of other inventions. On theother hand, FIG. 9A shows the separator 10 which is another mode of thepolymer electrolyte fuel cell material of the third invention. Theseparator 10 has, as shown in the drawing, a plurality of ridges 12, 16and a plurality of grooves 14, 18 in parallel with each other on the topsurface and back surface in an inside-out relation. As is shown in theenlarged view of FIG. 9B, the separator 10 comprises a plate material 1of approximately 0.2 mm thick composed of an austenitic stainless steel,and cover films 4 a, 4 b of 1 to 40 nm thick composed of Au (noblemetal) formed so as to cover the top surface 2 and back surface 3thereof. The thickness of the cover films 4 a, 4 b is specified withinthe above-described range because the thickness smaller than 1 nmdegrades the corrosion resistance, and the thickness exceeding 40 nmincreases the cost. The separator 10 is exposed, for a long duration oftime, to a sulfuric-acid and steamy environment of approximately 80° C.or above under power generation during which the fuel gas (hydrogen,methanol) or oxidizer gas (air, oxygen) flows through the grooves 14,18, so as to cause the oxidation and reduction reactions through thepolymer electrolyte film disposed in adjacent thereto.

As shown in an enlarged sectional view of FIG. 9C, the surface 2 of theplate material 1 has a moderate regular rough, so that the cover film 4a composed of Au, formed so as to cover the surface 2, also has amoderate surface 4 ay conforming thereto. The surface 4 ay of the coverfilm 4 a is compressed by rolling described later, so as to suppress thesurface roughness as expressed in R_(max) to as small as 1.5 μm or less.An unillustrated surface 4 by of the cover film 4 b on the back surface3 also has a similar surface roughness. Because the top surface 2 andback surface 3 are thus covered with the cover films 4 a, 4 b, of whichsurfaces 4 ay, 4 by have a surface roughness expressed in R_(max) of assmall as 1.5 μm or less, the separator 10 can exhibit an excellentcorrosion resistance in such environment for a long duration of time.

Next paragraphs will describe a first fabrication method of the thirdinvention for obtaining an elementary plate (polymer electrolyte fuelcell material) 8 of the separator 10, referring to FIG. 10 and FIG. 11(combination with the first invention also allowable of course). FIG.10A shows a section of the plate material 1 of 0.2 mm thick, composed ofthe austenitic stainless steel (SUS316L; C≦0.08 wt %, Si≦1.00 wt %,Mn≦2.00 wt %, P≦0.045 wt %, S≦0.030 wt %, Ni: 12.00 to 15.00 wt %, Cr:16.00 to 18.00 wt %, Mo: 2.00 to 3.00 wt %, and the balance of Fe),which corresponds with the Fe-base alloy of the third invention.

The top surface 2 and back surface 3 of the plate material 1 aresubjected to a publicly-known Au electroplating or Au electrolessplating (coverage step). This results in formation of the cover films 4a, 4 b of Au (noble metal) of approximately 40 nm thick, respectively onthe top surface 2 and back surface 3 of the plate material 1, to therebyobtain a stacked plate 5, as shown in FIG. 10B. As shown in an enlargedview of FIG. 10C, which is an enlargement of portion C surrounded by adashed line in FIG. 10B, the surface 4 ax of the Au film 4 a has aregular rough conforming to the regular rough of the surface 2 of theplate material 1 in the stacked plate 5, with an enhanced profile. Theregular rough on the surface 2 is produced due to transfer of regularroughs on the circumferential surface of the rolling roll, and loss ofthe metal component caused by surface treatment such as acid cleaning orby heat treatment such as annealing. The Au cover film 4 a conforms tothe regular rough of the surface 2 but is thicker on the projectedportions and thinner on the recessed portions, so that the surface 4 axthereof finally has a more emphasized profile. It is to be noted thatalso the Au cover film 4 b on the back surface 3 of the plate material 1has a similar regular rough on the surface 4 bx thereof.

Next, the stacked plate 5 covered with the Au cover films 4 a, 4 b onthe top and back surfaces 2, 3 thereof is subjected to cold rolling(rolling step) by allowing it to pass between a pair of rolls 6, 6 asshown in FIG. 11A. The draft herein is typically set to 1% or above, andmore specifically 10%. The surface roughness of the circumferentialsurface of the rolls 6, 6 is 1.5 μm or less expressed in R_(max). Thisproduces the elementary plate 8 slightly thinned as shown on the righthand side of FIG. 11A. In the rolling, the Au cover films 4 a, 4 b,which are relatively soft, are preferentially compressed. Averagethickness of the cover films 4 a, 4 b will be reduced nearly inproportion to the draft of the rolling. As shown in an enlarged view ofFIG. 11B, which is an enlargement of portion B surrounded by a dashedline in FIG. 11A, the surface 2 of the plate material 1 is slightlycompressed, so that also the regular rough thereof is smoothened to acorrespondent degree. On the other hand, the surface 4 ay of the Aucover film 4 a newly produced by the rolling is compressed andsmoothened to a considerable degree during the rolling. This isconsequently successful in suppressing the surface roughness asexpressed in R_(max) of the surface 4 ay to as small as 1.5 μm or less.

It is therefore made possible to fabricate the separator 10 excellent inthe corrosion resistance as described in the above, by subjecting theelementary plate 8 to plastic working using an unillustrated pressmachine, to thereby form a plurality of ridges 12, 16 and a plurality ofgrooves 14, 18. It is also allowable to fabricate a current collectorplate used for both ends of the fuel cell, by forming the Au cover film4 on either one of the top surface 2 and back surface 3 of the platematerial 1, which is followed by rolling and press forming to therebyobtain a predetermined geometry.

The plate material 1 may be composed of any stainless steels other thanthose described in the above, or other Fe-base alloy, Ni-base alloy, Tiand Ti alloy. The noble metal is not limited to Au, but also may be Ag,Pt, Pd, Rh or Ir, or alloys mainly composed of any of these elements. Onthe other hand, it is also allowable to fabricate the elementary plate8, similarly to the second fabrication method of the third invention, byforming the cover films 4 a, 4 b of a noble metal such as Au on the topsurface 2 and back surface 3 of the plate material 1 after thesmoothening step based on electrolytic polishing or rolling using therolls having a surface roughness as expressed in R_(max) of 1.5 μm orless.

(Fourth Invention)

This invention relates mainly to material characters, and will bedetailed later referring to experimental results. Specific examples ofthe metal separator for fuel cell and fuel cell using the same wereexplained previously referring to FIG. 1 and FIG. 2A to FIG. 2C, asembodiments common for those of other inventions.

EXAMPLES

Next paragraphs will describe results of our experiments conducted inorder to confirm the effects of the individual inventions.

(First Invention)

Each of metal bases having any of material compositions shown in Table 1was formed into a band form, and the Au plated film was formed thereonto a thickness up to 100 nm by the method shown in FIG. 3. The metalbase having the Au plated film formed thereon was then cut by the methodshown in FIG. 5A, and pressed to thereby fabricate a separator shown inFIG. 2A to FIG. 2C. The separator has a 50 mm×40 mm rectangular form.The width of the exposed surface of the metal base in the cutting planewas found to be 1 mm or less. Each thus-fabricated separator was thensubjected to a corrosion test in a sulfuric acid solution. Testconditions are as follows. That is, the separator was dipped in asulfuric acid solution of pH2 at 100° C. for 168 hours. The sulfuricacid atmosphere herein assimilates an environment in which the separatorused for the fuel cell shown in FIG. 1 can be exposed during operationof the fuel cell. The sample was then taken out, and evaluated foroccurrence of pinhole and crack, and the degree of corrosion anddiscoloration in the cutting plane (end face) portion of the separator,through observation of the outer appearance and discoloration of thesulfuric acid solution. Results are shown in Table 1. Evaluations weremade while marking those showing no corrosion nor discoloration of themetal base, and no discoloration of the sulfuric acid solution with ◯,and those showing such corrosion and discolorations with X. TABLE 1Chromium + Tested Molyb- metal Nickel Chromium Molybdenum Iron CopperTantalum Titanium Aluminum Corrosion test denum*3.3 base wt % wt % wt %wt % wt % wt % wt % wt % results wt % Titanium Titanium 100 ◯ 0 TitaniumTi—22V— 74 4 ◯ 0 alloy 4Al Chromium Chromium 100 ◯ 100 Austenitic 317J5L25 20 7 48 ◯ 43.1 SUS (904L) Austenitic 317L 14.39 18.65 3.25 63.71 ◯29.4 SUS Austenitic 317J1 13 17 3 67 ◯ 26.9 SUS Austenitic 310S 19.2224.7 56.08 ◯ 24.7 SUS Austenitic 316 12 17 2 69 ◯ 23.6 SUS Nickel-baseNCH1 78 21 ◯ 21 alloy Nickel-base I800 32 20.5 46 0.3 ◯ 20.5 alloyAustenitic 304 9 19 72 ◯ 19 SUS Austenitic 305 12 18 70 ◯ 18 SUSAustenitic XM7 9 18 69 3 ◯ 18 SUS Ferritic SUS 430 17 83 ◯ 17 AusteniticDSN8 14.24 16.06 69.7 ◯ 16.1 SUS Nickel-base I600 75.18 15.31 9.1 0.6 ◯15.3 alloy Nickel-base M400 65 2 32 X 0 alloy Nickel-base Nickel 100 X 0alloy Carbon Carbon 100 X 0 steel steel Aluminum 0.2 0.23 0.2 >99 X 0.2alloy A5052It was found from Table 1 that no corrosion or discoloration of themetal base were observed in the examples adopting Fe-base alloys andNi-base alloys which contain at least Cr and satisfyW_(Cr)+3.3W_(Mo)≧10. Similarly no corrosion and discoloration of themetal base were observed also for the case where the metal base wascomposed of a simple Cr. On the other hand, corrosion and discolorationof the metal base were observed for Cr-free, Ni-base alloy (M400),aluminum alloy (A5052), simple Ni and carbon steel. It was supposedthat, in the inventive examples, the passivation film was formed on theexposed surface of the metal base in the test environment, due toformation of a local cell between the metal base and Au plated film.

Next, SUS304 was adopted as a material for composing the metal base, andthe Au film of 100 nm thick was formed on the surface of the band-formedmetal base, according to a method similar to the above-described method.The band-formed metal base was then cut into a separator form by variousmethods of cutting, to thereby fabricate the separators. The width ofthe surface of the exposed metal base on the cutting plane of each ofthus-obtained separators was observed, to thereby obtain results shownin Table 2. The separators were then subjected to the corrosion testsimilarly to as described in the above. The results were combined andshown in Table 2. TABLE 2 Width of exposed surface Corrosion resistance0.05 mm  ◯ 0.1 mm ◯ 0.2 mm ◯ 0.5 mm ◯ 1.0 mm ◯ 2.0 mm X 5.0 mm X

As is known from Table 2, the separators having the width of exposedsurface of the metal base exceeding 1 mm in the cutting plane thereofshowed corrosion of the metal bases, but those having the width ofexposed surface of the metal base of 1 mm or less showed no corrosion ofthe metal bases at all.

Next, three materials of SUS316L, SUS304L and SUS430 were selected asmaterials for composing the metal base, and the Au plated film of 100 nmthick was formed on a 50 mm×40 mm metal base of 0.2 mm thick, whilevarying the ratio of coverage as 5%, 10%, 20%, 50%, 70% and 90%. Thecorrosion test was conducted similarly to as described in the above, andthe corrosion and discoloration were observed in the region where themetal base exposes. The corrosion and discoloration were observed forSUS316L having a large passivation performance (W_(Cr)+3.3W_(Mo)) undera ratio of coverage of 5%, but no more observed for 10% or above. On theother hand, the corrosion was no more observed for SUS304L having asmaller passivation performance under a ratio of coverage of 20% orabove, and the corrosion was no more observed for SUS430 having afurther smaller passivation performance under a ratio of coverage of 70%or above. In conclusion, the amount of formation of the Au plated filmnecessary for corrosion prevention largely depends on the passivationperformance of the metal base, and an appropriate selection of amaterial of the metal base makes it possible to further reduce the Auconsumption.

Next, SUS316L was adopted as a material for composing the metal base,and the band-formed metal bases were obtained by forming, on the entiresurface thereof, the Au plated film while varying the thickness thereofto 0.5 nm, 1 nm, 3 nm, 5 nm, 10 nm, 50 nm, 100 nm, 500 nm and 1000 nm.Each of the metal bases was then shaped into separators, and theseparators were then subjected to the corrosion test. It was found thatthe corrosion and discoloration were observed in the region where themetal base exposes under a film thickness of 0.5 nm, but no moreobserved under a film thickness of 1 nm or above.

(Second Invention)

Example 1

The second inventive examples and comparative example Steels(SUS304-base) having compositions shown in Table 3 below were melted andforged to thereby prepare ingots, and the ingots were further forged androlled to thereby manufacture steel plates of 0.2 mm thick. The steelplates were then subjected to solution treatment at 1,100° C., andpunched to produce 50×40 mm test pieces for the corrosion test. The testpieces were then subjected to the corrosion test by the proceduresdescribed below. Results are shown in Table 3. In the corrosion test,the above-described test piece was kept as being dipped in 0.4 liter (L)of a 0.1 wt % sulfuric acid solution (approximately pH2) boiled underreflux for 168 hours, and metal ions eluted into the solution wasanalyzed by atomic absorption spectrometry, and amount thereof wasexpressed in weight per 0.4 liter (L) of the solution. TABLE 3 Amount ofion elution Composition (wt %) (mg/0.4 liter) Judg- No. C Si Mn P S CuNi Cr Mo* N Nb A** Fe Cr Ni Cu Mo ment Inventive 1 0.072 0.59 0.76 0.0300.009 0.12 6.27 17.06 0.08 0.0300 — 24.4 10 2.4 2.2 <0.1 <0.1 ◯ Examples2 0.065 0.55 0.74 0.024 0.008 5.30 9.30 19.30 0.07 0.018 — 22.2 1.3 0.60.5 <0.1 <0.1 ◯ 3 0.056 0.72 0.96 0.022 0.002 0.51 8.67 18.41 0.460.0150 — 19.8 3.3 0.7 0.5 <0.1 <0.1 ◯ 4 0.050 0.77 0.95 0.024 0.002 1.058.55 18.38 0.48 0.0160 — 18.3 2.5 0.6 0.4 <0.1 <0.1 ◯ 5 0.068 0.62 0.760.016 0.006 2.06 10.27 18.42 0.29 0.0250 — 22.4 3.1 0.7 0.5 <0.1 <0.1 ◯6 0.052 0.56 0.80 0.026 0.007 0.13 10.20 18.12 0.08 0.0290 1.10 19.1 0.80.1 0.1 <0.1 <0.1 ◯ 7 0.066 0.66 0.74 0.016 0.006 4.08 10.24 18.96 0.280.0220 — 21.8 4.3 1.0 0.7 0.1 <0.1 ◯ 8 0.047 0.58 0.92 0.020 0.003 5.9812.12 18.52 0.16 0.0060 — 17.5 8.8 2.1 1.9 0.6 <0.1 ◯ 9 0.010 0.70 0.860.016 0.008 0.70 8.96 18.56 0.50 0.0200 — 7.8 2.6 0.6 0.4 <0.1 <0.1 ◯ 100.012 0.68 0.90 0.020 0.003 0.62 8.82 18.44 0.46 0.0180 0.86 8.6 0.6<0.1 <0.1 <0.1 <0.1 ◯ 11 0.016 0.30 0.32 0.022 0.004 2.01 10.30 18.280.30 0.0140 — 7.0 2.4 0.6 0.3 <0.1 <0.1 ◯ 12 0.009 0.17 0.02 0.005 0.0022.08 10.22 18.32 0.32 0.0110 — 2.9 0.9 0.2 0.1 <0.1 <0.1 ◯ 13 0.065 0.650.74 0.014 0.005 2.02 10.32 18.40 0.32 0.0190 0.40 21.3 1.8 0.5 0.3 <0.1<0.1 ◯ Compar- 1 0.075 0.55 0.72 0.029 0.009 0.05 6.22 17.11 0.14 0.0280— 24.9 101 22 22 <0.1 <0.1 X ative 2 0.045 0.56 0.90 0.020 0.003 8.0412.20 18.73 0.17 0.0070 — 16.9 24 5.9 1.6 1.2 <0.1 X Examples 3 0.0660.66 0.74 0.014 0.005 0.01 10.30 18.45 0.30 0.0220 — 21.6 168 42 28 <0.10.7 X 4 0.015 0.28 0.26 0.024 0.004 0.01 10.32 18.30 0.31 0.0140 — 6.5152 39 22 <0.1 0.7 X 5 0.008 0.15 0.02 0.004 0.002 0.01 10.20 18.40 0.390.0110 — 2.6 146 38 21 <0.1 0.6 X*Mo in an amount of 0.10 wt % is judged as an impurity/**A expresses a value calculated by a formula of 250 × [C %] + 5 × {Mn%} + 25 × [P %] + 200 × [S %].

As is known from Table 3, the second inventive examples showed an amountof Fe ion elution of 0.6 to 10 mg/0.4 L, an amount of Cr ion elution of2.4 mg/0.4 L or less, an amount of eluted Ni ion of 2.2 mg/0.4 L orless, an amount of Cu ion elution of 0.6 mg/0.4 L or less, and an amountof Mo ion elution of 0.1 mg/0.4 L or less. Of these, second inventiveexamples No. 11 and No. 12 which are equivalent to second inventiveexample No. 5 but lowered in the “A” value (a value calculated by theformula of 250×[C %]+5×{Mn %}+25×[P %]+200×[S %]), and the secondinventive example No. 13 which is equivalent to second inventive exampleNo. 5 but added with Nb, showed the amount of Fe ion elutionconsiderably lower than that of second inventive example No. 5. Effectof addition of Cu is obvious from comparison between second inventiveexample No. 1 and comparative example No. 1.

In contrast to this, comparative examples No. 1 and No. 3 to 5 having Cucontents lower than those of the second invention, and comparativeexample No. 2 having Cu content higher than that of the second inventionshowed all of the amount of elution of Fe ion, Cr ion and Ni ionapproximately 1.5 times as large as those of the second invention.Comparative examples No. 4 and No. 5 having an “A” value of 10 or below,but having Cu content smaller than those of the second invention showedall of the amount of elution of Fe ion, Cr ion and Ni ion approximately10 times or more as large as those of the second inventive examples.

Example 2

The second inventive examples and comparative example steels(SUSXM7-base) having compositions shown in Table 4 below were processedsimilarly to as described in Example 1, to thereby manufacture 50×40 mmsample steel plates for corrosion-resistant of 0.2 mm thick. The testpieces were then subjected to the corrosion test by the proceduresdescribed in the above. Results are shown in Table 4. TABLE 4 Amount ofion elution Composition (wt %) (mg/0.4 liter) Judg- No. C Si Mn P S CuNi Cr Mo* N Ti A** Fe Cr Ni Cu Mo ment Inventive 14 0.058 0.48 0.680.011 0.004 2.16 8.05 17.09 0.50 0.0200 — 19.0 5.4 1.2 0.6 <0.1 <0.1 ◯Examples 15 0.056 0.48 0.65 0.012 0.004 2.12 8.08 17.10 1.01 0.0210 —18.4 4.6 1.1 0.5 <0.1 <0.1 ◯ 16 0.066 0.38 0.78 0.028 0.006 3.84 10.1218.95 2.06 0.0060 — 22.2 5.2 1.5 0.8 <0.1 <0.1 ◯ 17 0.068 0.35 0.770.027 0.006 3.82 9.78 18.75 3.04 0.0050 — 22.7 6.8 2.0 1.1 0.2 0.3 ◯ 180.062 0.38 0.77 0.028 0.005 3.86 9.46 18.44 4.00 0.0070 — 21.1 9.9 2.91.6 0.4 0.6 ◯ 19 0.018 0.24 0.26 0.016 0.004 3.55 10.11 18.65 2.100.0130 — 7.0 1.8 0.5 0.3 <0.1 <0.1 ◯ 20 0.008 0.15 0.02 0.005 0.002 3.6210.16 18.70 2.13 0.0120 — 2.6 0.6 0.2 0.1 <0.1 <0.1 ◯ 21 0.063 0.32 0.760.025 0.005 3.80 10.08 18.92 2.02 0.0130 0.40 21.2 3.2 0.9 0.5 <0.1 <0.1◯ Compara- 6 0.056 0.47 0.68 0.016 0.005 2.12 8.12 17.16 0.01 0.0220 —18.8 186 44 35 10 <0.1 X tive 7 0.054 0.49 0.66 0.014 0.005 2.14 8.1817.08 0.10 0.0210 — 18.2 18 4.4 2.2 1.1 <0.1 X Examples 8 0.066 0.360.74 0.036 0.006 3.88 9.12 18.12 5.03 0.0060 — 22.1 18 5.5 2.9 0.6 1.5 X9 0.067 0.36 0.78 0.030 0.006 3.64 10.22 18.78 0.01 0.0080 — 22.6 62 1810 3.4 <0.1 X 10 0.017 0.25 0.24 0.015 0.004 3.45 10.06 18.66 0.010.0140 — 6.6 56 16 8.6 3.1 <0.1 X 11 0.007 0.16 0.02 0.004 0.002 3.6610.14 18.62 0.01 0.0130 — 2.4 50 15 7.7 2.8 <0.1 X*Mo in an amount of 0.10 wt % is judged as an impurity/**A expresses a value calculated by a formula of 250 × [C %] + 5 × {Mn%} + 25 × [P %] + 200 × [S %].

As is known from Table 4, the second inventive examples showed an amountof Fe ion elution of 0.6 to 9.9 mg/0.4 L, an amount of Cr ion elution of0.2 to 2.9 mg/0.4 L, an amount of eluted Ni ion of 0.1 to 1.6 mg/0.4 L,an amount of Cu ion elution of 0.4 mg/0.4 L or less, and an amount of Moion elution of 0.6 mg/0.4 L or less. Of these, second inventive examplesNo. 19 and No. 21 which are equivalent to second inventive example No.16 but lowered in the “A” value, and the second inventive example No. 21which is equivalent to second inventive example No. 16 but added withTi, showed the amount of Fe ion elution considerably lower than those ofthe other second inventive examples. Effect of addition of Mo is obviousfrom comparison between second inventive example No. 15 and comparativeexample No. 6.

In contrast to this, comparative examples No. 6, No. 7 and No. 9 to 11having Mo contents lower than those of the second invention, andcomparative example No. 8 having Mo content higher than that of thesecond invention showed all of the amount of elution of Fe ion, Cr ionand Ni ion approximately 1.5 times as large as those of the secondinventive examples. Comparative examples No. 10 and No. 11 having an “A”value of 10 or below, but having Mo content smaller than those of thesecond invention showed all of the amount of elution of Fe ion, Cr ionand Ni ion approximately 5 times or more as large as those of the secondinventive examples.

Example 3

The second inventive examples and comparative example Steels(SUS316-base) having compositions shown in Table 5 below were processedsimilarly to as described in Example 1, to thereby manufacture 50×40 mmsample steel plates for corrosion-resistant of 0.2 mm thick. The testpieces were then subjected to the corrosion test by the proceduresdescribed in the above. Results are shown in Table 5. TABLE 5 Amount ofion elution Composition (wt %) (mg/0.4 liter) Judg- No. C Si Mn P S CuNi Cr Mo* N Nb A** Fe Cr Ni Cu Mo ment Inventive 22 0.065 0.65 0.740.030 0.009 0.11 10.56 16.33 2.22 0.0290 — 22.5 10 2.2 1.4 <0.1 0.3 ◯Examples 23 0.022 0.73 0.97 0.025 0.006 0.50 12.22 17.56 2.12 0.0150 —12.2 1.0 0.2 0.2 <0.1 <0.1 ◯ 24 0.020 0.72 0.96 0.024 0.005 1.00 12.3217.54 2.10 0.0160 — 11.4 0.8 0.2 0.1 <0.1 <0.1 ◯ 25 0.055 0.44 0.680.030 0.007 2.02 13.66 18.02 1.32 0.0070 — 19.3 1.1 0.3 0.2 <0.1 <0.1 ◯26 0.054 0.46 0.66 0.028 0.007 4.03 13.56 18.00 1.35 0.0080 — 18.9 2.00.6 0.4 <0.1 <0.1 ◯ 27 0.068 0.72 0.47 0.016 0.005 6.00 14.32 18.41 3.580.0210 — 21.0 5.0 1.5 1.2 0.5 0.3 ◯ 28 0.020 0.26 0.27 0.023 0.002 2.0313.86 18.10 1.59 0.0110 — 7.3 0.6 0.2 0.1 <0.1 <0.1 ◯ 29 0.009 0.15 0.020.006 0.002 2.08 13.46 18.09 1.48 0.0120 — 2.9 0.2 0.3 0.2 <0.1 <0.1 ◯30 0.052 0.48 0.60 0.028 0.007 2.10 13.57 18.16 1.40 0.0140 1.10 18.10.8 0.2 0.2 <0.1 <0.1 ◯ Compara- 12 0.068 0.67 0.72 0.028 0.009 0.0510.52 16.23 2.23 0.0280 — 23.1 162 36 23 <0.1 4.5 X tive 13 0.053 0.480.72 0.030 0.006 0.01 13.56 18.00 1.38 0.0070 — 18.8 121 33 26 <0.1 2.3X Examples 14 0.018 0.28 0.24 0.020 0.003 0.01 13.72 18.11 1.47 0.0110 —6.8 110 30 23 <0.1 2.5 X 15 0.006 0.16 0.03 0.007 0.001 0.01 13.68 18.081.50 0.0120 — 2.0 102 28 22 <0.1 2.3 X*Mo in an amount of 0.10 wt % is judged as an impurity/**A expresses a value calculated by a formula of 250 × [C %] + 5 × {Mn%} + 25 × [P %] + 200 × [S %].

As is known from Table 5, the second inventive examples showed an amountof Fe ion elution of 0.2 to 10 mg/0.4 L, an amount of Cr ion elution of0.2 to 2.2 mg/0.4 L, and an amount of eluted Ni ion of 0.1 to 1.4 mg/0.4L. Of these, second inventive examples No. 28 and No. 29 which areequivalent to second inventive example No. 25 but lowered in the “A”value, and the second inventive example No. 31 which is equivalent tosecond inventive example No. 25 but added with Nb, showed the amount ofsuch as Fe ion elution considerably lower than those of the other secondinventive example No. 25. Effect of addition of Cu is obvious fromcomparison between second inventive example No. 22 and comparativeexample No. 12.

In contrast to this, comparative examples No. 12 to No. 11 having Cucontents lower than those of the second invention showed all of theamount of elution of Fe ion, Cr ion and Ni ion 10 times as large asthose of the second inventive examples. Comparative examples No. 14 andNo. 15 having “A” values of 10 or below, but having Cu content smallerthan those of the second invention showed all of the amount of elutionof Fe ion, Cr ion and Ni ion smaller than those for the examples having“A” value exceeding 10, but approximately 10 times or more as large asthose of the second inventive examples.

(Third Invention)

Next paragraphs will describe specific examples of the third inventiontogether with comparative examples.

Eight plate materials 1 composed of the above-described austeniticstainless steel (SUS316L: Fe-base alloy) of 40 mm wide, 50 mm long and0.2 mm thick were obtained. Surface roughness (R_(max)) of the topsurface 2 and back surface 3 were measured, and the results were listedin Table 6.

Of these, two plate materials (inventive examples 5, 6) 1 werepreliminarily smoothened on the top surfaces 2 and back surfaces 3 byelectrolytic polishing, and the surface roughness was measured.

The Au films 4 a, 4 b were then formed on the top surfaces 2 and backsurfaces 3 of eight plate materials 1 to a thickness of 20 nm under thesame plating conditions, to thereby obtain eight stacked plates 5.

Next, six stacked plates 5, excluding one of two smoothened platematerials (inventive example 6) and comparative example 2, weresubjected to a single pass of cold rolling under a draft of 10%, tothereby obtain the elementary plates 8. Surface roughness after therolling was measured, and the results were shown in Table 6.

Of six plate materials not being subjected to the smoothening process,the five subjected to rolling were named Examples 1 to 4 and ComparativeExample 1. The one subjected to both of the smoothening and rollingprocesses was named Example 5, and the one subjected to the smootheningprocess but not to the rolling process was named Example 6. In addition,the residual one subjected to neither of the smoothening process nor therolling process was named Comparative Example 2.

The above-described individual elementary plates 8 and stacked plates 5were subjected to the corrosion test.

In the corrosion test, each of the plates of the individual examples waskept as being dipped in 0.4 liter (L) of a 0.1% sulfuric acid solution(pH2) boiled under reflux for 168 hours (7 days), and metal ions elutedinto the solution was analyzed by atomic absorption spectrometry, andamount thereof was expressed in weight per 0.4 liter (L) of thesolution. Also these results were listed by the individual examples inTable 6. TABLE 6 Surface Surface roughness roughness before after Amountof Fe Amount of Ni plating rolling ion elution ion elution (R_(max) μm)(R_(max) μm) (mg/L) (mg/L) Example 1 2.2 0.2 0.02 0 Example 2 2.2 0.80.02 0 Example 3 2.2 1.2 0.07 0.01 Example 4 2.2 1.5 0.15 0.01 Example 51.2 0.2 0.01 0 Example 6 0.8 0.8 0.05 0 (not rolled) Comparative 2.2 1.80.19 0.02 example 1 Comparative 2.2 2.2 2.7 0.02 example 2 (not rolled)

As is known from Table 6, Examples 1 to 6 show amount of Fe ion elutionof 0.15 mg/liter or less, and amount of Ni ion elution of 0.01 mg/literor less, which are within the specified ranges. The plate materials ofthe Examples can therefore exhibit an excellent corrosion resistance ina reliable manner even when they are exposed, as the separator 10 orcurrent collector plate composed of the above-described cell material,to an extremely corrosive environment for a long duration of time.

In contrast to this, Comparative Example 1 showed both of amounts of Feion elution and Ni ion elution slightly exceeding the specified rangesdue to a surface roughness (R_(max)) after rolling of as large as 1.8μm, despite a surface roughness (R_(max)) before Au plating of 2.2 μm.

Comparative Example 2 which was subjected only to the Au plating but notto rolling or smoothing was found to be extremely increased both in theamounts of Fe ion elution and Ni ion elution.

Example 5 which was preliminarily subjected to the smoothening stepprior to the Au plating was found to have a surface roughness (R_(max))after Au plating of as small as 1.2 μm, and to have a surface roughness(R_(max)) after rolling of again as small as 0.2 μm, and was smallest ofall examples in the amounts of Fe ion elution and Ni ion elution.Example 6 which was preliminarily smoothened by electrolytic polishingso as to reduce the surface roughness (R_(max)) to as small as 0.8 μm,was found to fall in the above-described specified ranges even withoutthe rolling.

It will readily be understood that the results of Examples 1 to 6 provedthe effect of the third invention.

According to the polymer electrolyte fuel cell material of the thirdinvention, a planarized regular rough is formed on the surface of thecover film of noble metal conforming to the micro-irregularity on thesurface of the plate material, and the cover film of noble metal issmoothened as being expressed by a surface roughness (R_(max)) of assmall as 1.5 μm or less, so that the natural potential is averaged overthe entire surface. This makes it possible for the cell material toexhibit an excellent corrosion resistance even if it is exposed to acorrosive environment for a long duration of time.

The above-described cell material is also successful in exhibiting anexcellent corrosion resistance in a more reliable manner, if it isexposed for a long time, in a form of a separator for example, to anextremely corrosive environment.

According to the first method of manufacturing a polymer electrolytefuel cell material of the third invention, it is made possible tofabricate the cell material covered with the cover film of a noble metaland having a smooth surface in a reliable-and-efficient manner.

According to the method of manufacturing the cell material, it is madepossible to surely smoothen the cover film of a noble metal, which isformed conforming to the micro-irregularity on the surface of the platematerial, so as to reduce the surface roughness as expressed in R_(max)to as small as 1.5 μm or less.

According to the second method of manufacturing a polymer electrolytefuel cell material of the third invention, the surface of the platematerial is preliminarily planarized, so that the coverage by the noblemetal layer will be done in a smoothened manner.

(Fourth Invention)

Cleaning for removing foreign films was carried out by the wet processor dry process. First, representative process steps of the wet processare as follows:

1) degreasing: a material-to-be-processed is dipped in a solution, whichcontains 40 g/L of sodium orthosilicate and 1 g/L of a surfactantdissolved therein and is kept at 60° C., for approximately one minute;

2) cleaning and drying: the material-to-be-processed is subjected toultrasonic cleaning in pure water, and is allowed to stand in a dry air,or is blown with a dry nitrogen gas or the like;

3) removal of contamination film: a 10% sulfuric acid solution is keptat 60° C., and electrolysis is carried out therein while keeping thematerial-to-be-processed as an anode, under a current density ofapproximately 5 A/dm² for approximately one minute;

4) cleaning and drying: same as those described in the above;

5) activation: a 10% sulfuric acid solution is kept at 60° C., and thematerial-to-be-processed is dipped therein for approximately one minute;

6) cleaning and drying: same as those described in the above;

7) noble metal plating: electroplating is carried out in a plating bathcontaining a noble metal salt dissolved therein; and

8) cleaning and drying: same as those described in the above.

Representative process steps of the dry process are as follows:

1) degreasing: a material-to-be-processed is dipped in a solution, whichcontains 40 g/L of sodium orthosilicate and 1 g/L of a surfactantdissolved therein and is kept at 60° C., for approximately one minute;

2) cleaning and drying: the material-to-be-processed is subjected toultrasonic cleaning in pure water, and is allowed to stand in a dry air,or is blown with a dry nitrogen gas or the like;

3) evacuation: up to 1×10⁻⁶ Torr;

4) removal of contamination film: after the evacuation, argon gas at 5mTorr is introduced, ionized under a beam current of 250 mA, and is thenirradiated onto the surface of the material-to-be-processed forapproximately 5 minutes; and

5) formation of noble metal film: sputtering or vacuum evaporation inargon gas.

Some of the cleaning carried out in the Examples below may slightly bemodified, so that possible processes will be listed below:

A: same as the representative wet process described in the above;

B: in process step 3) “removal of contamination film” in method “A” inthe above, the material-to-be-processed is dipped in a 5% sulfuric acidsolution kept at room temperature for approximately 30 seconds;

C: in process step 3) “removal of contamination film” in method “A” inthe above, the material-to-be-processed is dipped in a 10% hydrochloricacid solution kept at room temperature for approximately 30 seconds;

D: same as the representative dry process described in the above; and

E: in process step 4) “removal of contamination film” in method “D” inthe above, after the evacuation, argon gas at 3 mTorr is introduced,ionized under a beam current of 100 mA, and is then irradiated onto thesurface of the material-to-be-processed for approximately 3 minutes.

Various austenitic stainless steels (austenitic ones for all) were usedas the metal base, cleaning was carried out according to any one ofmethods “A” to “E” listed in the above, and after elapse of apredetermined interval of time, a film of Au, Pt, Pd, Rh or Ru wasformed thereon by electroplating or sputtering. Species of the metalbase, cleaning methods, time interval, film forming methods and filmthickness are listed in Table 7.

The obtained corrosion-resistant conductive materials were subjected toAuger analysis, to thereby measure contents of C, P, O and S, which areimpurities in the noble metal film and intermediate layer, and tothereby find Cr/Fe ratio and Ni/Fe ratio of the intermediate layer. Thedipping test was then carried out in a boiling sulfuric acid of pH 2 for168 hours. Amount of Fe, Ni and Cr ions eluted into 400 ml of thesulfuric acid solution were measured, wherein those showing an amount ofFe elution exceeding 0.2 mg, or those having a total amount of Fe+Ni+Crelution exceeding 0.3 mg were judged as unacceptable. Results were shownin Table 8. TABLE 7 Film Classification Metal base Cleaning Noblethickness Interval No. SUS method metal Coverage method (nm) (min)Example 1 316L A Au electroplating 40 0.2 Example 2 316L A Auelectroplating 40 0.8 Example 3 316L A Au electroplating 10 0.4 Example4 316L A Au electroplating 80 0.4 Comparative 316L A Au electroplating40 1.5 Example 1 Comparative 316L B Au electroplating 40 0.4 Example 2Comparative 316L C Au electroplating 40 0.4 Example 3 Example 5 304 A Auelectroplating 60 0.5 Example 6 304L A Au electroplating 60 0.5 Example7 316 A Au electroplating 60 0.5 Example 8 XM7 A Au electroplating 600.5 Example 9 316J1L A Au electroplating 10 0.5 Example 10 317J1 A Auelectroplating 20 0.5 Example 11 431 A Au electroplating 80 0.2 Example12 316L D Au sputtering 40 0.1 Comparative 316L D Au sputtering 40 3.0Example 4 Comparative 316L E Au sputtering 40 0.2 Example 5 Example 13301 D Pt sputtering 40 0.1 Example 14 310S D Pd sputtering 40 0.1Example 15 347 D Rh sputtering 40 0.1 Example 16 316L D Ru sputtering 400.1

TABLE 8 Noble metal film layer and intermediate layer Maximum impurityconcentration Maximum concentration Amount of ion elution ClassificationC P O S Total ratio Fe Ni Cr Total No. (%) (%) (%) (%) (%) Cr/Fe Ni/Fe(mg) (mg) (mg) (mg) Judgment Example 1 1.0 0.9 0.0 0.0 1.9 0.7 0.9 0.040.01 0.01 0.06 ◯ Example 2 1.0 1.0 0.0 0.0 2.0 0.5 0.8 0.03 0.01 0.010.05 ◯ Example 3 1.2 1.2 0.2 0.3 0.9 2.9 0.8 0.15 0.03 0.02 0.20 ◯Example 4 1.0 1.1 0.0 0.0 2.1 0.8 0.8 0.04 0.01 0.01 0.06 ◯ Comparative2.8 1.2 1.6 0.3 5.9 0.7 0.9 0.28 0.03 0.02 0.33 X Example 1 Comparative4.0 3.0 0.7 1.6 9.3 2.8 1.4 0.34 0.09 0.10 0.53 X Example 2 Comparative1.1 1.1 0.4 0.9 3.5 3.1 2.2 0.22 0.06 0.06 0.34 X Example 3 Example 51.4 1.0 0.0 0.0 2.4 1.2 0.8 0.16 0.01 0.01 0.18 ◯ Example 6 1.0 1.0 0.00.0 2.0 0.9 0.9 0.05 0.01 0.01 0.07 ◯ Example 7 1.3 0.9 0.0 0.0 2.2 0.70.7 0.15 0.01 0.01 0.17 ◯ Example 8 1.0 1.1 0.0 0.0 2.1 0.6 0.6 0.050.01 0.01 0.07 ◯ Example 9 1.1 1.3 0.2 0.4 3.0 0.6 0.7 0.07 0.02 0.030.12 ◯ Example 10 1.2 1.1 0.1 0.2 2.6 0.7 0.6 0.04 0.01 0.01 0.06 ◯Example 11 1.1 0.8 0.2 0.1 2.2 0.7 0.0 0.11 0.00 0.05 0.16 ◯ Example 121.0 0.9 0.0 0.0 1.9 1.0 0.9 0.05 0.01 0.01 0.07 ◯ Comparative 8.0 6.03.0 2.0 19 2.8 1.4 0.50 0.12 0.13 0.75 X Example 4 Comparative 2.5 2.21.0 0.5 6.2 2.5 1.2 0.36 0.09 0.10 0.55 X Example 5 Example 13 1.1 0.90.0 0.0 2.0 1.0 0.9 0.08 0.02 0.02 0.12 ◯ Example 14 1.0 1.0 0.0 0.0 2.01.0 0.9 0.09 0.02 0.01 0.12 ◯ Example 15 1.2 0.9 0.0 0.0 2.1 1.0 0.90.09 0.02 0.01 0.12 ◯ Example 16 1.0 1.1 0.0 0.0 2.1 1.0 0.9 0.07 0.010.02 0.10 ◯

The present inventors revealed for the case where a thin film of noblemetal such as gold is formed on a metal base such as stainless steel,that properties of the thin film, in particular presence/absence andamount of pinholes and adhesiveness thereof to the base, distinctivelyvary depending on foreign matters which reside in the thin film, inparticular contents of C, P, O and S as impurities, and also dependingon composition of the intermediate layer which resides between the baseand the thin film. The present inventors also confirmed that this sortof influence becomes particularly large for the case where the noblemetal film is as extremely thin as 100 nm or less.

Based on the discovery, proposed is the fourth invention which ischaracterized in that it prevents re-contamination of the purifiedsurface of the base by carrying out the cleaning operation for removingforeign film contaminating the surface of the base and the succeedingthin film forming operation within a short interval of time, and therebysucceeded in forming the noble metal thin film which is extremely lessin the impurities, has almost no pinholes, has denseness, and shows adesirable adhesiveness to the base.

The fourth invention can therefore provide a corrosion-resistantconductive material, represented by a metal separator used in polymerelectrolyte fuel cells, which is excellent in the corrosion resistance,high in the electric conductivity and low in the contact resistance. Themetal separator shows a satisfactory electric conductivity and anexcellent corrosion resistance in a high-temperature condition of use,despite it only has, as being formed on the surface thereof, a noblemetal thin film of as thin as several ten nanometers. The cost thereofis in a level allowing an easy industrialization, by virtue of a smallconsumption of the noble metal.

1. A metal component for fuel cell, to be disposed in contact with amain cell unit comprising a polymer electrolyte film and a pair ofelectrodes holding it in between, configured as having a plate-formedmetal base composed of a metal less noble than Au, and an Au film formedon the main surface thereof, having a cutting plane formed as an endface stretched up to said main surface, the cutting plane having aregion of 1 mm or less in width having said metal base exposes therein.2. A metal component for fuel cell, to be disposed in contact with amain cell unit comprising a polymer electrolyte film and a pair ofelectrodes holding it in between, configured as having an Au film formedon the main surface of a plate-formed metal base composed of a metalless noble than Au, and said metal base being cut along a plannedcutting line reflecting a contour of said component.
 3. The metalcomponent for fuel cell as claimed in claim 1, wherein said electrodehas a plate form and is in contact with said polymer electrolyte film ona first main surface thereof, and said metal component is composed as aseparator disposed in contact with said electrode on a second mainsurface thereof, having a regular rough on the main surface opposing tosaid electrode, projected portions of said regular rough being broughtinto contact with said electrode, and recessed portions of said regularrough serving as a gas flow path through which a fuel gas or an oxidizergas is supplied to said electrode.
 4. A metal component for fuel cellavailable as a separator disposed in contact with a second main surfaceof a plate-formed electrode which is disposed in contact with a polymerelectrolyte film as an electrolyte on a first main surface thereof,having a regular rough on the main surface, opposing to said electrode,of a plate-formed metal base composed of a metal less noble than Au, topportions of projected portions of said regular rough being brought intocontact with said electrode, and recessed portions of said regular roughserving as a gas flow path through which a fuel gas or an oxidizer gasis supplied to said electrode, wherein said metal base has an Au film of1 to 500 nm thick formed on both of the tip surface of said projectedportions brought into contact with said electrode, and the main surfaceregion other than said tip surface.
 5. The metal component for fuel cellas claimed in claim 4, wherein said Au film has exposed regions of saidbase formed therein in a discrete manner.
 6. (canceled)
 7. (canceled) 8.(canceled)
 9. (canceled)
 10. (canceled)
 11. (canceled)
 12. An austeniticstainless steel for polymer electrolyte fuel cell, consistingessentially of, in % by weight (same will apply hereinafter), Cu:0.10-6.00%, Ni: 6.00-13.00%, Cr: 16.00-20.00%, N: 0.005-0.30%, Si: 1.00%or less, Mn: 1.00% or less, and the balance of Fe and inevitableimpurities.
 13. An austenitic stainless steel for polymer electrolytefuel cell, consisting essentially of Cu: 0.10-6.00%, Ni: 6.00-13.00%,Cr: 16.00-20.00%, Mo: 0.10-4.00%, N: 0.005-0.30%, Si: 1.00% or less, Mn:1.00% or less, and the balance of Fe and inevitable impurities.
 14. Anaustenitic stainless steel for polymer electrolyte fuel cell, consistingessentially of Cu: 0.10-6.00%, Ni: 10.00-15.00%, Cr: 16.00-18.50%, Mo:1.00-4.00%, N: 0.005-0.30%, Si: 1.00% or less, Mn: 1.00% or less, andthe balance of Fe and inevitable impurities.
 15. An austenitic stainlesssteel for polymer electrolyte fuel cell, consisting essentially of Cu:0.10-6.00%, Ni: 6.00-13.00%, Cr: 16.00-20.00% and N: 0.005-0.30%, andalso of C: less than 0.02%, Si: 1.00% or less, Mn: 1.00% or less, P:0.030% or less and S: 0.005% or less, satisfying a relation of 250×[C%]+5×[Mn %]+25×[P %]+200×[S %]<10, and the balance of Fe and inevitableimpurities.
 16. An austenitic stainless steel for polymer electrolytefuel cell, consisting essentially of Cu: 0.10-6.00%, Ni: 6.00-13.00%,Cr: 16.00-20.00%, Mo: 0.10-4.00% and N: 0.005-0.30%, and also of C: lessthan 0.02%, Si: 1.00% or less, Mn: 1.00% or less, P: 0.030% or less andS: 0.005% or less, satisfying a relation of 250×[C %]+5×[Mn %]+25×[P%]+200×[S %]<10, and the balance of Fe and inevitable impurities.
 17. Anaustenitic stainless steel for polymer electrolyte fuel cell, consistingessentially of Cu: 0.10-6.00%, Ni: 10.00-15.00%, Cr: 16.00-18.50%, Mo:1.004.00% and N: 0.005-0.30%, and also of C: less than 0.02%, Si: 1.00%or less, Mn: 1.00% or less, P: 0.030% or less and S: 0.005% or less,satisfying a relation of 250×[C %]+5×[Mn %]+25×[P %]+200×[S %]<10, andthe balance of Fe and inevitable impurities.
 18. (canceled) 19.(canceled)
 20. (canceled)
 21. (canceled)
 22. A polymer electrolyte fuelcell material comprising a plate material composed of an Fe-base alloy,Ni-base alloy, Ti or Ti-base alloy, and a cover film of a noble metalcovering the surface thereof, wherein the cover film on the platematerial has a surface roughness as expressed in R_(max) of 1.5 μm orless.
 23. The polymer electrolyte fuel cell material as claimed in claim22, wherein said cell material shows, in a metal ion release test, anamount of Fe ion elution of 0.15 mg/0.4 liter or less, and an amount ofNi ion elution of 0.01 mg/0.4 liter or less.
 24. (canceled) 25.(canceled)
 26. (canceled)
 27. A metal component for fuel cell configuredby using the polymer electrolyte fuel cell material as claimed in claim22, and to be disposed in contact with a main cell unit comprising apolymer electrolyte film as an electrolyte and a pair of electrodesholding it in between.
 28. The metal component for fuel cell as claimedin claim 27, wherein said electrode has a plate form and is in contactwith said polymer electrolyte film on a first main surface thereof, andsaid metal component is composed as a separator disposed in contact withsaid electrode on a second main surface thereof, having a regular roughon the main surface opposing to said electrode, projected portions ofsaid regular rough being brought into contact with said electrode, andrecessed portions of said regular rough serving as a gas flow paththrough which a fuel gas or an oxidizer gas is supplied to saidelectrode.
 29. (canceled)
 30. A corrosion-resistant conductive componentcomprising a metal base and a noble metal film of 100 nm thick or lessformed on at least a part of the surface of said metal component, saidnoble metal layer and an intermediate layer formed between said base andsaid noble metal layer having impurity contents of C: 1.5% or less, P:1.5% or less, O: 1.5% or less and S: 1.5% or less, and being restrictedto C+P+O+S: 4.0% or less.
 31. The corrosion-resistant conductivecomponent as claimed in claim 30, wherein said metal base is a stainlesssteel.
 32. The corrosion-resistant conductive component as claimed inclaim 31, wherein said stainless steel is an austenitic stainless steel.33. The corrosion-resistant conductive component as claimed in claim 32,wherein said noble metal layer and said intermediate layer have amaximum Cr/Fe ratio of 3 or less, and a maximum Ni/Fe ratio of 2 orless.
 34. The corrosion-resistant conductive material as claimed inclaim 30, wherein a noble metal composing said noble metal film is anyone element selected from Au, Pt, Pd, Rh and Ru, mixtures of theseelements, and alloys mainly composed of these elements.
 35. (canceled)36. The corrosion-resistant conductive component as claimed in claim 30,being configured as a metal separator for fuel cell.
 37. (canceled) 38.The metal component for fuel cell as claimed in claim 2, wherein saidelectrode has a plate form and is in contact with said polymerelectrolyte film on a first main surface thereof, and said metalcomponent is composed as a separator disposed in contact with saidelectrode on a second main surface thereof, having a regular rough onthe main surface opposing to said electrode, projected portions of saidregular rough being brought into contact with said electrode, andrecessed portions of said regular rough serving as a gas flow paththrough which a fuel gas or an oxidizer gas is supplied to saidelectrode.
 39. A metal component for fuel cell configured by using thepolymer electrolyte fuel cell material as claimed in claim 23, and to bedisposed in contact with a main cell unit comprising a polymerelectrolyte film as an electrolyte and a pair of electrodes holding itin between.